Modified phosphinimine catalysts for olefin polymerization

ABSTRACT

Olefin polymerization is carried out with a supported phosphinimine catalyst which has been treated with a long chain substituted amine compound.

CROSS REFERENCE TO RELATED PATENT APPLICATION

This application is a continuation-in-part of U.S. application Ser. No.13/200,144, filed on Sep. 19, 2011, which claims priority to and thebenefit of Canadian Application No. 2,742,461, filed Jun. 9, 2011.

FIELD

The present invention relates to supported phosphinimine catalysts,which when treated with appropriate amounts of a suitable catalystmodifier, have improved activity and which produce improved polyethylenewith improved reactor operability. Catalyst modifiers comprise at leastone long chain substituted amine and are present in a phosphiniminebased polymerization catalyst prior to its entry into a polymerizationreactor.

BACKGROUND

Gas phase olefin polymerization with single site catalysts has been awell-established art field since the invention of metallocene catalystsover two decades ago. Although single site polymerization catalysts(such as metallocene catalysts, constrained geometry catalysts, andphosphinimine catalysts) are often chosen for their very high activity,the use of such catalysts can lead to reactor fouling especially in afluidized bed gas phase reactor. Such fouling may include polymeragglomeration, sheeting, or chunking, and may ultimately require reactorshut down.

In order to improve reactor operability, several specialized catalystpreparative methods, operating conditions, and additives have been usedto modify the performance of metallocenes and to reduce reactor fouling.

European Patent Application No. 630,910 discusses reversibly reducingthe activity of a metallocene catalyst using a Lewis base compound suchas, for example, an amine compound.

Long chain substituted alkanolamine compounds in particular, have beenused in combination with metallocenes to reduce the amount of reactorfouling in fluidized bed polymerization processes. The use ofsubstituted alkanolamines in combination with metallocene catalysts toimprove reactor operability and reduce static levels is described inEuropean Patent Application No. 811,638 and in U.S. Pat. Nos. 5,712,352;6,201,076; 6,476,165; 6,180,729; 6,977,283; 6,114,479; 6,140,432;6,124,230; 6,117,955; 5,763,543; and 6,180,736. Alkanolamines have beenadded to a metallocene catalyst prior to addition to a reaction zone, asdescribed in U.S. Pat. Nos. 6,140,432; 6,124,230 and 6,114,479.Alkanolamines have also been added directly to a reactor or otherassociated parts of a fluidized bed reactor processes such as therecycle stream loop as is taught in European Patent Application No.811,638 and in U.S. Pat. No. 6,180,729, respectively.

There has been no systematic exploration of the effect of long chainsubstituted amines, including monoalkanolamines and dialkanolamines, onsupported phosphinimine catalysts.

SUMMARY

We now report that a supported phosphinimine catalyst which has beentreated with appropriate amounts of a suitable catalyst modifier,operates at higher productivity levels and with reduced associatedreactor fouling. When specific levels of catalyst modifier were added toa supported phosphinimine catalyst, the productivity could be increasedby more than 10%. Surprisingly, treatment of a supported phosphiniminecatalyst with a suitable catalyst modifier, also lead to modified, evenimproved copolymer products, which had increased branching homogeneityand could be used to make cast film having lower gel levels.

In some embodiments, the present invention is directed to the use of acatalyst modifier comprising at least one long-chain amine. Addition ofa catalyst modifier to a supported phosphinimine catalyst for use in agas phase polymerization reactor, gives very good reactor operability,improved polymer product and few reactor discontinuity events. Anexample of a suitable catalyst modifier is a long chain amine compoundsuch as a C₆ to C₃₀ hydrocarbyl substituted dialkanolamine.

Provided is a process for polymerizing ethylene and optionally an alphaolefin in a reactor with a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier comprises at leastone long-chain amine compound and is present in an amount to give fromabout 1.0 to about 4.0 weight percent of catalyst modifier based on theweight of i), ii) and iii) of the polymerization catalyst.

Provided is a process for polymerizing ethylene and optionally an alphaolefin in a reactor, the process comprising introducing a polymerizationcatalyst into the reactor, the polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from about0.5 to about 4.5 weight percent based on the weight of i), ii) and iii)of the polymerization catalyst and comprises a compound having theformula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and nis an integer from 1 to 30; when x is 0, y is 2 and each n isindependently an integer from 1 to 30.

Provided is a polymerization process comprising contacting ethylene andat least one alpha olefin with a polymerization catalyst in a gas phasereactor, the polymerization catalyst comprising: i) a phosphiniminecatalyst; ii) an inert support; iii) a cocatalyst; and iv) a catalystmodifier; wherein the catalyst modifier is present in from about 0.5 toabout 4.5 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and n is aninteger from 1 to 30; when x is 0, y is 2 and each n is independently aninteger from 1 to 30; and wherein the phosphinimine catalyst has theformula: (L)((t-Bu)₃P═N)TiX₂, where L is a ligand selected fromcyclopentadienyl, substituted cyclopentadienyl, indenyl, and substitutedindenyl; and X is an activatable ligand.

Provided is an olefin polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from about0.5 to about 4.5 weight percent based on the weight of i), ii) and iii)of the polymerization catalyst and comprises a compound having theformula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and nis an integer from 1 to 30; when x is 0, y is 2 and each n isindependently an integer from 1 to 30.

Provided is an olefin polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from about0.25 to about 6.0 weight percent based on the weight of i), ii) and iii)of the polymerization catalyst and comprises a compound having theformula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and nis an integer from 1 to 30; when x is 0, y is 2 and each n isindependently an integer from 1 to 30; wherein the phosphiniminecatalyst has the formula: (L)((t-Bu)₃P═N)TiX₂, where L is a ligandselected from cyclopentadienyl, substituted cyclopentadienyl, indenyl,and substituted indenyl; and X is an activatable ligand.

In an embodiment of the invention, a catalyst modifier is present infrom about 1.0 to about 4.0 weight percent based on the weight of i),ii) and iii) of a polymerization catalyst comprising: i) a phosphiniminecatalyst; ii) an inert support; iii) a cocatalyst; and iv) a catalystmodifier.

In an embodiment of the invention, a catalyst modifier is present infrom about 1.5 to about 3.5 weight percent based on the weight of i),ii) and iii) of a polymerization catalyst comprising: i) a phosphiniminecatalyst; ii) an inert support; iii) a cocatalyst; and iv) a catalystmodifier.

In an embodiment of the invention, a catalyst modifier comprises atleast one compound represented by the formula:R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) where R¹ is a hydrocarbyl group havingfrom 5 to 30 carbon atoms, and n and m are integers from 1 to 20.

In an embodiment of the invention, a catalyst modifier comprises atleast one compound represented by the formula: R¹N((CH₂)_(n)OH)₂ whereR¹ is an hydrocarbyl group having from 6 to 30 carbon atoms, and each nis an integer from 1-20.

In an embodiment of the invention, a catalyst modifier comprises atleast one compound represented by the formula: R¹N(CH₂CH₂OH)₂ where R¹is a hydrocarbyl group having from 6 to 30 carbon atoms.

In an embodiment of the invention, a phosphinimine catalyst has theformula: (L)(Pl)MX₂, where M is Ti, Zr or Hf; Pl is a phosphinimineligand having the formula R₃P═N—, where R is independently selected fromhydrogen, halogen, and C₁-C₂₀ hydrocarbyl; L is a ligand selected fromcyclopentadienyl, substituted cyclopentadienyl, indenyl, substitutedindenyl, fluorenyl, and substituted fluorenyl; and X is an activatableligand.

In an embodiment of the invention, a phosphinimine catalyst has theformula: (L)((t-Bu)₃P═N)TiX₂, where L is a ligand selected fromcyclopentadienyl, substituted cyclopentadienyl, indenyl, and substitutedindenyl; and X is an activatable ligand.

In an embodiment of the invention, a cocatalyst is selected from ionicactivators, alkylaluminoxanes and mixtures thereof.

In an embodiment of the invention, the polymerization process is a gasphase polymerization process carried out in a fluidized bed reactor.

Provided is a polymerization process comprising contacting ethylene andat least one alpha olefin with a polymerization catalyst in a gas phasereactor, the polymerization catalyst comprising: i) a phosphiniminecatalyst, ii) an inert support, iii) a cocatalyst, and iv) a catalystmodifier; wherein the catalyst modifier is present in from about 0.25 toabout 6.0 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and n is aninteger from 1 to 30; when x is 0, y is 2 and each n is independently aninteger from 1 to 30; wherein the phosphinimine catalyst has theformula: (L)((t-Bu)₃P═N)TiX₂, where L is a cyclopentadienyl ligand, asubstituted cyclopentadienyl ligand, an indenyl ligand, or a substitutedindenyl ligand; and X is an activatable ligand; and wherein the processfurther comprises feeding the catalyst modifier to the gas phase reactorin an amount of 50 ppm or less (based on the weight of the polymerproduced).

In an embodiment of the invention, the catalyst modifier present in thepolymerization catalyst and fed to the gas phase reactor comprises atleast one compound represented by the formula:R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) where R¹ is a hydrocarbyl group havingfrom 5 to 30 carbon atoms, and n and m are integers from 1 to 20.

In an embodiment of the invention, the catalyst modifier present in thepolymerization catalyst and fed to the gas phase reactor comprises atleast one compound represented by the formula: R¹N((CH₂)_(n)OH)₂ whereR¹ is a hydrocarbyl group having from 6 to 30 carbon atoms, and each nis independently an integer from 1 to 20.

In an embodiment of the invention, the catalyst modifier present in thepolymerization catalyst and fed to the gas phase reactor comprises atleast one compound represented by the formula: R¹N((CH₂)_(n)OH)₂ whereR¹ is a hydrocarbyl group having from 6 to 30 carbon atoms, and each nis 2 or 3.

In an embodiment of the invention, the catalyst modifier present in thepolymerization catalyst and fed to the gas phase reactor comprises atleast one compound represented by the formula: R¹N(CH₂CH₂OH)₂ where R¹is a hydrocarbyl group having from 8 to 22 carbon atoms.

In an embodiment of the invention, the catalyst modifier present in thepolymerization catalyst and fed to the gas phase reactor comprises acompound represented by the formula: C₁₈H₃₇N(CH₂CH₂OH)₂.

In an embodiment of the invention, the catalyst modifier present in thepolymerization catalyst and fed to the gas phase reactor comprisescompounds represented by the formulas: C₁₃H₂₇N(CH₂CH₂OH)₂ andC₁₅H₃₁N(CH₂CH₂OH)₂.

In an embodiment of the invention, the catalyst modifier present in thepolymerization catalyst and fed to the gas phase reactor is a mixture ofcompounds represented by the formula: R¹N(CH₂CH₂OH)₂ where R¹ is ahydrocarbyl group having from 8 to 18 carbon atoms.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows how the productivity of the polymerization catalystimproves when different levels and type of catalyst modifier areincluded in the catalyst formulation. Poly. Run Nos. 7, 9 and 11 forvarious levels of Armostat-1800, relative to baseline Run No. 6. Poly.Run No. 2 for Atmer-163 relative to baseline Run No. 1. Baselinepolymerization runs are where there is no catalyst modifier included inthe catalyst formulation.

FIG. 2 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofa catalyst not treated with a catalyst modifier (baseline Run No. 1).

FIG. 3 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofcatalyst treated with 1.5 wt % of Atmer-163.

FIG. 4 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofa catalyst not treated with a catalyst modifier (baseline Run No. 6).

FIG. 5 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofcatalyst treated with 1.5 wt % of Armostat-1800.

FIG. 6 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofcatalyst treated with 2.5 wt % of Armostat-1800.

FIG. 7 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofcatalyst treated with 3.5 wt % of Armostat-1800.

FIG. 8 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofa catalyst not treated with a catalyst modifier (baseline Run No. 13).

FIG. 9 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence of25 ppm of Atmer-163 added directly to the reactor (based on the weightof the polymer produced).

FIG. 10 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofa catalyst not treated with a catalyst modifier (baseline Run No. 16).

FIG. 11 shows the reactor static in nanoamps (nA) over time, measuredusing a Correstat 3410 static probe located in the reactor during apolymerization run. The polymerization is carried out in the presence ofcatalyst treated with 2.5 wt % of Armostat-1800 (Run No. 17).

DETAILED DESCRIPTION

In the present invention, a “catalyst modifier” comprises at least onelong chain amine compound which, when added to a phosphinimine basedpolymerization catalyst in appropriate amounts, can reduce, prevent ormitigate at least one: of fouling, sheeting, temperature excursions, andstatic level of a material in polymerization reactor; and/or can alterthe properties of copolymer product obtained in a polymerizationprocess.

The Catalyst Modifier

In some embodiments, carrying out a polymerization reaction with aphosphinimine based polymerization catalyst, which has been treated witha catalyst modifier comprising at least one long chain amine compound,allows for high production rates in a gas phase polymerization reactorwith reduction of at least one of: reactor fouling, reactor staticlevels, catalyst static levels, and reactor temperature excursions.Alterations or improvements to product polymer, and reduction in castfilm gel counts are also obtained.

The catalyst modifier employed as disclosed herein comprises a longchain amine compound. As used herein, the terms “long chain substitutedamine” or “long chain amine” are defined as tri-coordinate nitrogencompounds (i.e., amine based compounds) containing at least onehydrocarbyl group having at least 5 carbon atoms, or in some embodimentsfrom 6 to 30 carbon atoms. The terms “hydrocarbyl” or “hydrocarbylgroup” includes branched or straight chain hydrocarbyl groups which maybe fully saturated groups (i.e., have no double or triple bondingmoieties) or which may be partially unsaturated (i.e., they may have oneor more double or triple bonding moieties). The long chain hydrocarbylgroup may also contain unsaturation in the form of aromatic ringmoieties attached to or part of the main chain. In some embodiments, thelong chain amine (i.e., the tri-coordinate nitrogen compound) will alsohave at least one heteroatom containing hydrocarbyl group. Suchheteroatom containing hydrocarbyl groups can be branched or straightchain hydrocarbyl groups or substituted hydrocarbyl groups having one ormore carbon atoms and at least one heteroatom. Heteroatom containinghydrocarbyl groups may also contain unsaturated moieties. Suitableheteroatoms include for example, oxygen, nitrogen, phosphorus or sulfur.Other groups which may be attached to nitrogen in a long chainsubstituted amine compound are generally selected from hydrocarbylgroups having one or more carbon atoms and/or a hydrogen group (H).

In embodiments of the invention, the long chain amine is a long chainsubstituted monoalkanolamine, or a long chain substituteddialkanolamine. These amines have one or two alcoholhydrocarbyl groups,respectively, as well as a hydrocarbyl group having at least 5 carbons.

In an embodiment of the invention, the catalyst modifier employedcomprises at least one long chain amine compound represented by theformula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and nis an integer from 1 to 30; when x is 0, y is 2 and each n isindependently an integer from 1 to 30.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted monoalkanolamine represented by theformula R¹R²N((CH₂)_(n)OH) where R¹ is a hydrocarbyl group having from 5to 30 carbon atoms, R² is a hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, and n is an integer from 1-20.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, and n and m are integers from 1-20.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N((CH₂)_(n)OH)₂ where R¹ is a hydrocarbyl group having from 6to 30 carbon atoms, and n is an integer from 1-20.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N((CH₂)_(n)OH)₂ where R¹ is a hydrocarbyl group having from 6to 30 carbon atoms, and n is 2 or 3.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N((CH₂)_(n)OH)₂ where R¹ is a linear hydrocarbyl group havingfrom 6 to 30 carbon atoms, and n is 2 or 3.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N(CH₂CH—₂OH)₂ where R¹ is a linear hydrocarbyl group havingfrom 6 to 30 carbon atoms.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N(CH₂CH—₂OH)₂ where R¹ is a linear, saturated alkyl grouphaving from 6 to 30 carbon atoms.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having from 8 to22 carbon atoms.

In an embodiment of the invention, the catalyst modifier comprises along chain substituted dialkanolamine represented by the formula:C₁₈H₃₇N(CH₂CH₂OH)₂.

In an embodiment of the invention, the catalyst modifier comprises longchain substituted dialkanolamines represented by the formulas:C₁₃H₂₇N(CH₂CH₂OH)₂ and C₁₅H₃₁N(CH₂CH₂OH)₂.

In an embodiment of the invention, the catalyst modifier comprises amixture of long chain substituted dialkanolamines represented by theformula: R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having from 8 to18 carbon atoms.

Non limiting examples of catalyst modifiers which can be used in thepresent invention are Kemamine AS-990™, Kemamine AS-650™,Armostat-1800™, bis-hydroxy-cocoamine, 2,2′-octadecyl-amino-bisethanol,and Atmer-163™.

The long chain substituted amine may also be apolyoxyethylenehydrocarbyl amine.

In an embodiment of the invention, the catalyst modifier comprises apolyoxyethylenehydrocarbyl amine represented by the formula:R¹N((CH₂CH₂O)_(n)H)((CH₂CH₂O)_(m)H), where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbons, and n and m are integers from 1-10 orhigher (i.e., polymeric).

The Polymerization Catalyst

In some embodiments, the (olefin) polymerization catalyst comprises: i)a phosphinimine catalyst, ii) an inert support, iii) a cocatalyst, andiv) a catalyst modifier.

The Phosphinimine Catalyst

Some non-limiting examples of phosphinimine catalysts can be found inU.S. Pat. Nos. 6,342,463; 6,235,672; 6,372,864; 6,984,695; 6,063,879;6,777,509 and 6,277,931 all of which are incorporated by referenceherein.

Preferably, the phosphinimine catalyst is based on metals from group 4,which includes titanium, hafnium and zirconium. The most preferredphosphinimine catalysts are group 4 metal complexes in their highestoxidation state.

The phosphinimine catalysts described herein, usually require activationby one or more cocatalytic or activator species in order to providepolymer from olefins.

A phosphinimine catalyst is a compound (typically, an organometalliccompound) based on a group 3, 4 or 5 metal and which is characterized ashaving at least one phosphinimine ligand. Any compounds/complexes havinga phosphinimine ligand and which display catalytic activity for ethylene(co)polymerization may be called “phosphinimine catalysts”.

In an embodiment of the invention, a phosphinimine catalyst is definedby the formula: (L)_(n)(Pl)_(m)MX_(p) where M is a transition metalselected from Ti, Hf, Zr; Pl is a phosphinimine ligand; L is acyclopentadienyl-type ligand or a heteroatom ligand; X is an activatableligand; m is 1 or 2; n is 0 or 1; and p is determined by the valency ofthe metal M. In some embodiments, m is 1, n is 1 and p is 2.

In an embodiment of the invention, a phosphinimine catalyst is definedby the formula: (L)(Pl)MX₂ where M is a transition metal selected fromTi, Hf, Zr; Pl is a phosphinimine ligand; L is a cyclopentadienyl-typeligand; and X is an activatable ligand.

The phosphinimine ligand is defined by the formula: R₃P═N—, where Nbonds to the metal, and wherein each R is independently selected from ahydrogen atom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which areunsubstituted or further substituted by one or more halogen atoms and/orC₁₋₂₀ alkyl radical; C₁₋₈ alkoxy radical; C₆₋₁₀ aryl or aryloxy radical(the aryl or aryloxy radical optionally being unsubstituted or furthersubstituted by one or more halogen atoms and/or C₁₋₂₀ alkyl radical);amido radical; silyl radical of the formula: —SiR′₃ wherein each R′ isindependently selected from hydrogen, a C₁₋₈ alkyl or alkoxy radical,C₆₋₁₀ aryl or aryloxy radicals; and germanyl radical of the formula:—GeR′₃ wherein R′ is as defined above.

In an embodiment of the invention, the phosphinimine ligand is chosen sothat each R is a hydrocarbyl radical. In a particular embodiment of theinvention, the phosphinimine ligand is tri-(tertiarybutyl)phosphinimine(i.e., where each R is a tertiary butyl group, or “t-Bu” for short).

In an embodiment of the invention, the phosphinimine catalyst is a group4 compound/complex which contains one phosphinimine ligand (as describedabove) and one ligand L which is either a cyclopentadienyl-type ligandor a heteroatom ligand.

As used herein, the term “cyclopentadienyl-type” ligand is meant toinclude ligands which contain at least one five-carbon ring which isbonded to the metal via eta-5 (or, in some cases, eta-3) bonding. Thus,the term “cyclopentadienyl-type” includes, for example, unsubstitutedcyclopentadienyl, singly or multiply substituted cyclopentadienyl,unsubstituted indenyl, singly or multiply substituted indenyl,unsubstituted fluorenyl and singly or multiply substituted fluorenyl.Hydrogenated versions of indenyl and fluorenyl ligands are alsocontemplated for use in the current invention, so long as thefive-carbon ring which bonds to the metal via eta-5 (or, in some casesmeta-3) bonding remains intact. Substituents for a cyclopentadienylligand, an indenyl ligand (or hydrogenated version thereof) and afluorenyl ligand (or hydrogenated version thereof) may be selected froma C₁₋₃₀ hydrocarbyl radical (which hydrocarbyl radical may beunsubstituted or further substituted by, for example, a halide and/or ahydrocarbyl group; for example, a suitable substituted C₁₋₃₀ hydrocarbylradical is a pentafluorobenzyl group such as —CH₂C₆F₅); a halogen atom;a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl or aryloxy radical (each of whichmay be further substituted by, for example, a halide and/or ahydrocarbyl group; for example, a suitable C₆₋₁₀ aryl group is aperfluoroaryl group such as —C₆F₅); an amido radical which isunsubstituted or substituted by up to two C₁₋₈ alkyl radicals; aphosphido radical which is unsubstituted or substituted by up to twoC₁₋₈ alkyl radicals; a silyl radical of the formula —Si(R′)₃ whereineach R′ is independently selected from hydrogen, a C₁₋₈ alkyl or alkoxyradical, C₆₋₁₀ aryl or aryloxy radicals; and a germanyl radical of theformula —Ge(R′)₃ wherein R′ is as defined directly above.

As used herein, the term “heteroatom ligand” refers to a ligand whichcontains at least one heteroatom selected from boron, nitrogen, oxygen,silicon, phosphorus or sulfur. The heteroatom ligand may be sigma orpi-bonded to the metal. Exemplary heteroatom ligands include but are notlimited to “silicon containing” ligands, “amido” ligands, “alkoxy”ligands, “boron heterocycle” ligands and “phosphole” ligands.

Silicon containing ligands are defined by the formula:-(μ)SiR^(x)R^(y)R^(z) where the “-” denotes a bond to the transitionmetal and p is sulfur or oxygen. The substituents on the Si atom, namelyR^(x), R^(y) and R^(z) are required in order to satisfy the bondingorbital of the Si atom. The use of any particular substituent R^(x),R^(y) or R^(z) is not especially important. In an embodiment of theinvention, each of R^(x), R^(y) and R^(z) is a C₁₋₂ hydrocarbyl group(i.e., methyl or ethyl) simply because such materials are readilysynthesized from commercially available materials.

The term “amido” is meant to convey its broad, conventional meaning.Thus, these ligands are characterized by (a) a metal-nitrogen bond and(b) the presence of two substituents (which are typically simple alkylor silyl groups) on the nitrogen atom.

The term “alkoxy” is also intended to convey its conventional meaning.Thus, these ligands are characterized by (a) a metal oxygen bond, and(b) the presence of a hydrocarbyl group bonded to the oxygen atom. Thehydrocarbyl group may be a ring structure and may optionally besubstituted (e.g., 2,6 di-tertiary butyl phenoxy).

The “boron heterocyclic” ligands are characterized by the presence of aboron atom in a closed ring ligand. This definition includesheterocyclic ligands which also contain a nitrogen atom in the ring.These ligands are well known to those skilled in the art of olefinpolymerization and are fully described in the literature (see, forexample, U.S. Pat. Nos. 5,637,659 and 5,554,775 and the references citedtherein).

The term “phosphole” is also meant to convey its conventional meaning.“Phospholes” are cyclic dienyl structures having four carbon atoms andone phosphorus atom in the closed ring. The simplest phosphole is C₄PH₄(which is analogous to cyclopentadiene with one carbon in the ring beingreplaced by phosphorus). The phosphole ligands may be substituted with,for example, C₁₋₂₀ hydrocarbyl radicals (which may, optionally, containhalogen substituents); phosphido radicals; amido radicals; silyl oralkoxy radicals. Phosphole ligands are also well known to those skilledin the art of olefin polymerization and are described as such in U.S.Pat. No. 5,434,116.

The term “activatable ligand” refers to a ligand which may be activatedby a cocatalyst (also referred to as an “activator”), to facilitateolefin polymerization. An activatable ligand X may be cleaved from themetal center M via a protonolysis reaction or abstracted from the metalcenter M by suitable acidic or electrophilic catalyst activatorcompounds (also known as “co-catalyst” compounds) respectively, examplesof which are described below. The activatable ligand X may also betransformed into another ligand which is cleaved or abstracted from themetal center M (e.g., a halide may be converted to an alkyl group).Without wishing to be bound by any single theory, protonolysis orabstraction reactions generate an active “cationic” metal center whichcan polymerize olefins. In embodiments of the present invention, theactivatable ligand, X is independently selected from a hydrogen atom; ahalogen atom; a C₁₋₁₀ hydrocarbyl radical; a C₁₋₁₀ alkoxy radical; aC₆₋₁₀ aryl oxide radical, each of which said hydrocarbyl, alkoxy, andaryl oxide radicals may be unsubstituted by or further substituted by ahalogen atom, a C₁₋₈alkyl radical, a C₁₋₈ alkoxy radical, a C₈₋₁₀ arylor aryloxy radical; an amido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals; and a phosphido radicalwhich is unsubstituted or substituted by up to two C₁₋₈ alkyl radicals.Two activatable X ligands may also be joined to one another and form forexample, a substituted or unsubstituted diene ligand (i.e., 1,3-diene);or a delocalized heteroatom containing group such as an acetate group.

The number of activatable ligands depends upon the valency of the metaland the valency of the activatable ligand. The preferred phosphiniminecatalysts are based on group 4 metals in their highest oxidation state(i.e., 4⁺). Particularly suitable activatable ligands are monoanionicsuch as a halide (e.g., chloride) or a hydrocarbyl (e.g., methyl,benzyl).

In some instances, the metal of the phosphinimine catalyst may not be inthe highest oxidation state. For example, a titanium (III) componentwould contain only one activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula, (L)(Pl)MX₂, where M is Ti, Zr or Hf; Pl is a phosphinimineligand having the formula R₃P═N—, where R is independently selected fromhydrogen, halogen, and C₁-C₂₀ hydrocarbyl; L is a ligand selected fromcyclopentadienyl, substituted cyclopentadienyl, indenyl, substitutedindenyl, fluorenyl, and substituted fluorenyl; and X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula, (L)(Pl)TiX₂, where Pl is a phosphinimine ligand having theformula R₃P═N—, where R is independently selected from hydrogen,halogen, and C₁-C₂₀ hydrocarbyl; L is a ligand selected fromcyclopentadienyl, substituted cyclopentadienyl, indenyl, substitutedindenyl, fluorenyl, and substituted fluorenyl; and X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (L)((t-Bu)₃P═N)TiX₂, where L is a ligand selected fromcyclopentadienyl, substituted cyclopentadienyl, indenyl, and substitutedindenyl; and X is an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (L)((t-Bu)₃P═N)TiX₂, where L is a ligand selected from asubstituted cyclopentadienyl and substituted indenyl; and X is anactivatable ligand.

In an embodiment of the invention, the phosphinimine catalyst contains aphosphinimine ligand, a cyclopentadienyl ligand (“Cp” for short) and twochloride or two methyl ligands bonded to the group 4 metal.

In an embodiment of the invention, the phosphinimine catalyst contains aphosphinimine ligand, a singly or multiply substituted cyclopentadienylligand and two chloride or two methyl ligands bonded to the group 4metal.

In an embodiment of the invention, the phosphinimine catalyst contains aphosphinimine ligand, a perfluoroaryl substituted cyclopentadienylligand and two chloride or two methyl ligands bonded to the group 4metal.

In an embodiment of the invention, the phosphinimine catalyst contains aphosphinimine ligand, a perfluorophenyl substituted cyclopentadienylligand (i.e., Cp-C₆F₅) and two chloride or two methyl ligands bonded tothe group 4 metal.

In an embodiment of the invention, the phosphinimine catalyst contains a1,2-substituted cyclopentadienyl ligand and a phosphinimine ligand whichis substituted by three tertiary butyl substituents.

In an embodiment of the invention, the phosphinimine catalyst contains a1,2 substituted cyclopentadienyl ligand (e.g., a 1,2-(R*)(Ar—F)Cp) wherethe substituents are selected from R* a hydrocarbyl group, and Ar—F aperfluorinated aryl group, a 2,6 (i.e., ortho) fluoro substituted phenylgroup, a 2,4,6 (i.e., ortho/para) fluoro substituted phenyl group, or a2,3,5,6 (i.e., ortho/meta) fluoro substituted phenyl group respectively.

In the present invention, 1,2 substituted cyclopentadienyl ligands suchas, for example 1,2-(R*)(Ar—F)Cp ligands may contain as impurities 1,3substituted analogues such as for example 1,3-(R*)(Ar—F)Cp ligands.Hence, phosphinimine catalysts having a 1,2 substituted Cp ligand maycontain as an impurity, a phosphinimine catalyst having a 1,3substituted Cp ligand. Alternatively, the current invention contemplatesthe use of 1,3 substituted Cp ligands as well as the use of mixtures ofvarying amounts of 1,2 and 1,3 substituted Cp ligands to givephosphinimine catalysts having 1,3 substituted Cp ligands or mixedphosphinimine catalysts having 1,2 and 1,3 substituted Cp ligands.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1,2-(R*)(Ar—F)Cp)M(N═P(t-Bu)₃)X₂ where R* is a hydrocarbylgroup; Ar—F is a perfluorinated aryl group, a 2,6 (i.e., ortho) fluorosubstituted phenyl group, a 2,4,6 (i.e., ortho/para) fluoro substitutedphenyl group, or a 2,3,5,6 (i.e., ortho/meta) fluoro substituted phenylgroup; M is Ti, Zr or Hf; and X is an activatable ligand. In anembodiment of the invention, the phosphinimine catalyst has the formula:(1,2-(R*)(Ar—F)Cp)M(N═P(t-Bu)₃)X₂ where R* is an alkyl group; Ar—F is aperfluorinated aryl group, a 2,6 (i.e., ortho) fluoro substituted phenylgroup, a 2,4,6 (i.e., ortho/para) fluoro substituted phenyl group or a2,3,5,6 (i.e., ortho/meta) fluoro substituted phenyl group; M is Ti, Zror Hf; and X is an activatable ligand. In an embodiment of theinvention, the phosphinimine catalyst has the formula:(1,2-(R*)(Ar—F)Cp)M(N═P(t-Bu)₃)X₂ where R* is a hydrocarbyl group havingfrom 1 to 20 carbons; Ar—F is a perfluorinated aryl group; M is Ti, Zror Hf; and X is an activatable ligand. In an embodiment of theinvention, the phosphinimine catalyst has the formula:(1,2-(R*)(Ar—F)Cp)M(N═P(t-Bu)₃)X₂ where R* is a straight chain alkylgroup; Ar—F is a perfluorinated aryl group, a 2,6 (i.e., ortho) fluorosubstituted phenyl group, a 2,4,6 (i.e., ortho/para) fluoro substitutedphenyl group, or a 2,3,5,6 (i.e., ortho/meta) fluoro substituted phenylgroup; M is Ti, Zr or Hf; and X is an activatable ligand. In anembodiment of the invention, the phosphinimine catalyst has the formula:(1,2-(n-R*)(Ar—F)Cp)Ti(N═P(t-Bu)₃)X₂ where R* is a straight chain alkylgroup; Ar—F is a perfluorinated aryl group; M is Ti, Zr or Hf; and X isan activatable ligand. In an embodiment of the invention, thephosphinimine catalyst has the formula:(1,2-(R*)(C₆F₅)Cp)M(N═P(t-Bu)₃)X₂ where R* is a hydrocarbyl group having1 to 20 carbon atoms; M is Ti, Zr or Hf; and X is an activatable ligand.In an embodiment of the invention, the phosphinimine catalyst has theformula: (1,2-(n-R*)(C₆F₅)Cp)M(N═P(t-Bu)₃)X₂ where R* is a straightchain alkyl group; M is Ti, Zr or Hf; and X is an activatable ligand. Infurther embodiments, M is Ti and R* is any one of a methyl, ethyl,n-propyl, n-butyl, n-penty, n-hexyl, n-heptyl, and n-octyl group. Infurther embodiments, X is chloride or methide.

The term “perfluorinated aryl group” means that each hydrogen atomattached to a carbon atom in an aryl group has been replaced with afluorine atom as is well understood in the art (e.g., a perfluorinatedphenyl group or substituent has the formula —C₆F₅). In embodiments ofthe invention, Ar—F is selected from the group comprising perfluorinatedphenyl or perfluorinated naphthyl groups.

Some phosphinimine catalysts which may be used in the present inventioninclude: ((C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂;(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂,(1,2-(n-butyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ and(1,2-(n-hexyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂.

In an embodiment of the invention, the phosphinimine catalyst will havea single or multiply substituted indenyl ligand and a phosphinimineligand which is substituted by three tertiary butyl substituents.

An indenyl ligand (or “Ind” for short) as defined in the presentinvention will have framework carbon atoms with the numbering schemeprovided below, so the location of a substituent can be readilyidentified.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand and a phosphinimine ligand which issubstituted by three tertiary butyl substituents.

In an embodiment of the invention, the phosphinimine catalyst will havea singly or multiply substituted indenyl ligand where the substituent isselected from a substituted or unsubstituted alkyl group, a substitutedor an unsubstituted aryl group, and a substituted or unsubstitutedbenzyl (e.g., C₆H₅CH₂—) group. Suitable substituents for the alkyl, arylor benzyl group may be selected from alkyl groups, aryl groups, alkoxygroups, aryloxy groups, alkylaryl groups (e.g., a benzyl group),arylalkyl groups and halide groups.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, R^(¥)-Indenyl, where the R^(¥)substituent is a substituted or unsubstituted alkyl group, a substitutedor an unsubstituted aryl group, or a substituted or unsubstituted benzylgroup. Suitable substituents for an R^(¥) alkyl, R^(¥) aryl or R^(¥)benzyl group may be selected from alkyl groups, aryl groups, alkoxygroups, aryloxy groups, alkylaryl groups (e.g., a benzyl group),arylalkyl groups and halide groups.

In an embodiment of the invention, the phosphinimine catalyst will havean indenyl ligand having at least a 1-position substituent (1-R^(¥))where the substituent R^(¥) is a substituted or unsubstituted alkylgroup, a substituted or an unsubstituted aryl group, or a substituted orunsubstituted benzyl group. Suitable substituents for an R^(¥) alkyl,R^(¥) aryl or R^(¥) benzyl group may be selected from alkyl groups, arylgroups, alkoxy groups, aryloxy groups, alkylaryl groups (e.g., a benzylgroup), arylalkyl groups and halide groups.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R^(¥)-Indenyl where thesubstituent R^(¥) is in the 1-position of the indenyl ligand and is asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedaryl group, or a substituted or an unsubstituted benzyl group. Suitablesubstituents for an R^(¥) alkyl, R^(¥) aryl or R^(¥) benzyl group may beselected from alkyl groups, aryl groups, alkoxy groups, aryloxy groups,alkylaryl groups (e.g., a benzyl group), arylalkyl groups and halidegroups.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R^(¥)-Indenyl, where thesubstituent R^(¥) is a (partially/fully) halide substituted alkyl group,a (partially/fully) halide substituted benzyl group, or a(partially/fully) halide substituted aryl group.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R^(¥)-Indenyl, where thesubstituent R^(¥) is a (partially/fully) halide substituted benzylgroup.

When present on an indenyl ligand, a benzyl group can be partially orfully substituted by halide atoms, preferably fluoride atoms. The arylgroup of the benzyl group may be a perfluorinated aryl group, a 2,6(i.e., ortho) fluoro substituted phenyl group, 2,4,6 (i.e., ortho/para)fluoro substituted phenyl group or a 2,3,5,6 (i.e., ortho/meta) fluorosubstituted phenyl group respectively. The benzyl group is, in anembodiment of the invention, located at the 1 position of the indenylligand.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R^(¥)-Indenyl, where thesubstituent R^(¥) is a pentafluorobenzyl (C₆F₅CH₂—) group.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R^(¥)-(Ind))M(N═P(t-Bu)₃)X₂ where R^(¥) is a substituted orunsubstituted alkyl group, a substituted or an unsubstituted aryl group,or a substituted or unsubstituted benzyl group, wherein substituents forthe alkyl, aryl or benzyl group are selected from alkyl, aryl, alkoxy,aryloxy, alkylaryl, arylalkyl and halide substituents; M is Ti, Zr orHf; and X is an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R^(¥)-(Ind))M(N═P(t-Bu)₃)X₂ where R^(¥) is an alkyl group,an aryl group or a benzyl group and wherein each of the alkyl group, thearyl group, and the benzyl group may be unsubstituted or substituted byat least one fluoride atom; M is Ti, Zr or Hf; and X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R^(¥)-(Ind))M(N═P(t-Bu)₃)X₂ where R^(¥) is an alkyl group,an aryl group or a benzyl group and wherein each of the alkyl group, thearyl group, and the benzyl group may be unsubstituted or substituted byat least one halide atom; M is Ti, Zr or Hf; and X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R^(¥)-(Ind))Ti(N═P(t-Bu)₃)X₂ where R^(¥) is an alkyl group,an aryl group or a benzyl group and wherein each of the alkyl group, thearyl group, and the benzyl group may be unsubstituted or substituted byat least one fluoride atom; and X is an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-C₆F₅CH₂—Ind)M(N═P(t-Bu)₃)X₂, where M is Ti, Zr or Hf; and Xis an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-C₆F₅CH₂—Ind)Ti(N═P(t-Bu)₃)X₂, where X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-C₆F₅CH₂—Ind)Ti(N═P(t-Bu)₃)Cl₂.

The Cocatalyst

In the present invention, the phosphinimine catalyst is used incombination with at least one activator (or “cocatalyst”) to form anactive polymerization catalyst system for olefin polymerization.Activators (i.e., cocatalysts) include ionic activator cocatalysts andhydrocarbyl aluminoxane cocatalysts.

The activator used to activate the phosphinimine catalyst can be anysuitable activator including one or more activators selected fromalkylaluminoxanes and ionic activators, optionally together with analkylating agent.

The alkylaluminoxanes are complex aluminum compounds of the formula: R³₂Al¹O(R³Al¹O)_(m)Al¹R³ ₂, wherein each R³ is independently selected fromC₁₋₂₀ hydrocarbyl radicals and m is from 3 to 50. Optionally a hinderedphenol can be added to the alkylaluminoxane to provide a molar ratio ofAl¹:hindered phenol of from about 2:1 to about 5:1 when the hinderedphenol is present.

In an embodiment of the invention, R³ of the alkylaluminoxane, is amethyl radical and m is from 10 to 40.

The alkylaluminoxanes are typically used in substantial molar excesscompared to the amount of group 4 transition metal in the phosphiniminecatalyst. The Al¹:group 4 transition metal molar ratios are from 10:1 to10,000:1, preferably about 30:1 to 500:1.

In an embodiment of the invention, the catalyst activator ismethylaluminoxane (MAO).

In an embodiment of the invention, the catalyst activator is modifiedmethylaluminoxane (MMAO).

It is well known in the art, that the alkylaluminoxane can serve dualroles as both an alkylator and an activator. Hence, an alkylaluminoxaneactivator is often used in combination with activatable ligands such ashalogens.

Alternatively, the activator of the present invention may be acombination of an alkylating agent (which may also serve as a scavenger)with an activator capable of ionizing the group 4 metal of thephosphinimine catalyst (i.e., an ionic activator). In this context, theactivator can be chosen from one or more alkylaluminoxane and/or anionic activator.

When present, the alkylating agent may be selected from (R⁴)_(p)MgX²_(2-p) wherein X² is a halide and each R⁴ is independently selected fromC₁₋₁₀ alkyl radicals and p is 1 or 2; R⁴Li wherein in R⁴ is as definedabove, (R⁴)_(q)ZnX² _(2-q) wherein R⁴ is as defined above, X² is halogenand q is 1 or 2; (R⁴)_(s)Al²X² _(3-s) wherein R⁴ is as defined above, X²is halogen and s is an integer from 1 to 3. In some embodiments, in theabove compounds R⁴ is a C₁₋₄ alkyl radical, and X² is chlorine.Commercially available compounds include triethyl aluminum (TEAL),diethyl aluminum chloride (DEAC), dibutyl magnesium ((Bu)₂Mg), and butylethyl magnesium (BuEtMg or BuMgEt).

The ionic activator may be selected from the group consisting of: (i)compounds of the formula [R⁵]⁺[B(R⁶)₄]⁻ wherein B is a boron atom, R⁵ isa cyclic C₅₋₇ aromatic cation or a triphenyl methyl cation and each R⁶is independently selected from phenyl radicals which are unsubstitutedor substituted with from 3 to 5 substituents selected from a fluorineatom, a C₁₋₄ alkyl or alkoxy radical which is unsubstituted orsubstituted by a fluorine atom; and a silyl radical of the formula—Si—(R⁷)₃; wherein each R⁷ is independently selected from a hydrogenatom and a C₁₋₄ alkyl radical; and (ii) compounds of the formula[(R⁸)_(t)ZH]⁺[B(R⁶)₄]⁻ wherein B is a boron atom, H is a hydrogen atom,Z is a nitrogen atom or phosphorus atom, t is 2 or 3 and R⁸ is selectedfrom C₁₋₅ alkyl radicals, a phenyl radical which is unsubstituted orsubstituted by up to three C₁₋₄ alkyl radicals, or one R⁸ taken togetherwith a nitrogen atom may form an anilinium radical and R⁶ is as definedabove; and (iii) compounds of the formula B(R⁶)₃ wherein R⁶ is asdefined above.

In some embodiments, in the above compounds R⁶ is a pentafluorophenylradical, and R⁵ is a triphenylmethyl cation, Z is a nitrogen atom and R⁸is a C₁₋₄ alkyl radical or one R⁸ taken together with a nitrogen atomforms an anilinium radical (e.g., PhR⁸ ₂NH⁺, which is substituted by twoR⁸ radicals such as for example two C₁₋₄ alkyl radicals).

Examples of compounds capable of ionizing the phosphinimine catalystinclude the following compounds: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra)phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate, benzene (diazonium)tetrakispentafluorophenyl borate, tropilliumphenyltris-pentafluorophenyl borate, triphenylmethyliumphenyltrispentafluorophenyl borate, benzene (diazonium)phenyltrispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene (diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene (diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, trophenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene (diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene (diazonium)tetrakis(2,3,4,5-tetrafluorophenyl)borate.

Commercially available activators which are capable of ionizing thegroup 4 metal of the phosphinimine catalyst include:N,N-dimethylaniliniumtetrakispentafluorophenyl borate(“[Me₂NHPh][B(C₆F₅)₄]”); triphenylmethylium tetrakispentafluorophenylborate (“[Ph₃C][B(C₆F₅)₄]”); and trispentafluorophenyl boron and MAO(methylaluminoxane) and MMAO (modified methylaluminoxane).

The ionic activators compounds may be used in amounts which provide amolar ratio of group 4 transition metal to boron that will be from 1:1to 1:6.

Optionally, mixtures of alkylaluminoxanes and ionic activators can beused as activators in the polymerization catalyst.

The Inert Support

In the present invention, the phosphinimine catalyst is supported on aninert support. The support used herein can be any support known in theart to be suitable for use with polymerization catalysts. For example,the support can be any porous or non-porous support material, such astalc, inorganic oxides, inorganic chlorides, aluminophosphates (i.e.,AlPO₄) and polymer supports (e.g., polystyrene, etc.). Examples ofsupports include Group 2, 3, 4, 5, 13 and 14 metal oxides generally,silica, alumina, silica-alumina, magnesium oxide, magnesium chloride,zirconia, titania, clay (e.g., montmorillonite) and mixtures thereof.

Agglomerate supports such as agglomerates of silica and clay may also beused as a support in the current invention.

Supports are generally used in calcined form. An inorganic oxidesupport, for example, will contain acidic surface hydroxyl groups whichwill react with a polymerization catalyst. Prior to use, the inorganicoxide may be dehydrated to remove water and to reduce the concentrationof surface hydroxyl groups. Calcination or dehydration of a support iswell known in the art. In embodiments of the invention, the support iscalcined at temperatures above 200° C., or above 300° C., or above, 400°C., or above 500° C. In other embodiments, the support is calcined atfrom about 500° C. to about 1000° C., or from about 600° C. to about900° C. The resulting support may be free of adsorbed water and may havea surface hydroxyl content from about 0.1 to 5 mmol/g of support, orfrom 0.5 to 3 mmol/g. The amount of hydroxyl groups in a silica supportmay be determined according to the method disclosed by J. B. Peri and A.L. Hensley Jr., in J. Phys. Chem., 72 (8), 1968, pg. 2926.

The support material, especially an inorganic oxide, such as silica,typically has a surface area of from about 10 to about 700 m²/g, a porevolume in the range from about 0.1 to about 4.0 cc/g and an averageparticle size of from about 5 to about 500 prin. In a specificembodiment, the support material has a surface area of from about 50 toabout 500 m²/g, a pore volume in the range from about 0.5 to about 3.5cc/g and an average particle size of from about 10 to about 200 μm. Inanother specific embodiment the support material has a surface area offrom about 100 to about 400 m²/g, a pore volume in the range from about0.8 to about 3.0 cc/g and an average particle size of from about 5 toabout 100 μm.

The support material, especially an inorganic oxide, such as silica,typically has an average pore size (i.e., pore diameter) of from about10 to about 1000 Angstroms (Å). In a specific embodiment, the supportmaterial has an average pore size of from about 50 to about 500 Å. Inanother specific embodiment, the support material has an average poresize of from about 75 to about 350 Å.

The surface area and pore volume of a support may be determined bynitrogen adsorption according to B.E.T. techniques, which are well knownin the art and are described in the Journal of the American ChemicalSociety, 1938, v 60, pg. 309-319.

A silica support which is suitable for use in the present invention hasa high surface area and is amorphous. By way of example, useful silicasare commercially available under the trademark of Sylopol® 958, 955 and2408 from Davison Catalysts, a Division of W. R. Grace and Company andES-70W by PQ Corporation.

Agglomerate supports comprising a clay mineral and an inorganic oxide,may be prepared using a number techniques well known in the artincluding pelletizing, extrusion, drying or precipitation, spray-drying,shaping into beads in a rotating coating drum, and the like. Anodulization technique may also be used. Methods to make agglomeratesupports comprising a clay mineral and an inorganic oxide includespray-drying a slurry of a clay mineral and an inorganic oxide. Methodsto make agglomerate supports comprising a clay mineral and an inorganicoxide are disclosed in U.S. Pat. Nos. 6,686,306; 6,399,535; 6,734,131;6,559,090 and 6,968,375.

An agglomerate of clay and inorganic oxide which may be useful in thecurrent invention may have the following properties: a surface area offrom about 20 to about 800 m²/g, preferably from 50 to about 600 m²/g;particles with a bulk density of from about 0.15 to about 1 g/mL,preferably from about 0.20 to about 0.75 g/mL; an average pore diameterof from about 30 to about 300 Angstroms (Å), preferably from about 60 toabout 150 Å; a total pore volume of from about 0.10 to about 2.0 cc/g,preferably from about 0.5 to about 1.8 cc/g; and an average particlesize of from about 4 to 150 microns (μm), preferably from about 8 to 100microns.

Optionally, a support, for example a silica support, may be treated withone or more salts of the type: Zr(SO₄)₂.4H₂O, ZrO(NO₃)₂, and Fe(NO₃)₃ astaught in CA Patent Application No. 2,716,772 to the same applicant.Supports that have been otherwise chemically treated are alsocontemplated for use with the catalysts and processes of the presentinvention.

Without wishing to be bound by theory, Zr(SO₄)₂.4H₂O and ZrO(NO₃)₂ mayeach act as a source of zirconium oxide (i.e. ZrO₂) which may form forexample after calcinations temperatures are employed. Alternately, theZr(SO₄)₂.4H₂O can be used to add Zr(SO₄)₂ to an inert support ifsuitably high calcinations temperatures (those which promote formationof zirconium oxide) are not employed.

The present invention is not limited to any particular procedure forsupporting the phosphinimine catalyst or the cocatalyst. Processes fordepositing a phosphinimine catalyst complex and/or a cocatalyst on asupport are well known in the art (for some non-limiting examples ofcatalyst supporting methods, see “Supported Catalysts” by James H. Clarkand Duncan J. Macquarrie, published online Nov. 15, 2002 in theKirk-Othmer Encyclopedia of Chemical Technology Copyright© 2001 by JohnWiley & Sons, Inc.; for some non-limiting methods to support a singlesite catalyst see U.S. Pat. No. 5,965,677). For example, thephosphinimine catalyst may be added to a support by co-precipitationwith the support material. The cocatalyst can be added to a supportbefore and/or after the phosphinimine catalyst or together with thephosphinimine catalyst (i.e., the phosphinimine catalyst may be mixedwith a cocatalyst in a suitable solvent or diluents and the mixtureadded to a support). Optionally, the cocatalyst can be added to asupported phosphinimine catalyst in situ or on route to a reactor. Thephosphinimine catalyst and/or cocatalyst may be slurried or dissolved ina suitable diluent or solvent respectively and then added to a support.Suitable solvents or diluents include but are not limited tohydrocarbons and mineral oil. The phosphinimine catalyst may be added tothe solid support, in the form of a solid, solution or slurry, followedby the addition of the cocatalyst in solid form or as a solution orslurry. The cocatalyst may be added to the solid support, in the form ofa solid, solution or slurry, followed by the addition of thephosphinimine catalyst in solid form or as a solution or slurry.Phosphinimine catalyst, cocatalyst, and support can be mixed together inthe presence or absence of a diluent or solvent, but use of diluent(s)or solvent(s) is preferred.

The loading of the phosphinimine catalyst on the support is notspecifically defined, but by way of non-limiting example can be fromabout 0.005 to 1.0, or from about 0.010 to 0.50, or from about 0.015 to0.40, or from about 0.015 to 0.39, or from about 0.015 to 0.37, or fromabout 0.015 to 0.035 mmol of the phosphinimine catalyst per gram ofsupport. In further embodiments of the invention, the loading of thephosphinimine catalyst on the support may be from about 0.020 to 0.031mmol, or from about 0.025 to 0.0305 mmol of the phosphinimine catalystper gram of support.

In embodiments of the invention, a titanium based phosphinimine catalystwill be added to the inert support so as to give from 0.01 to 2.5% ofTi, or from 0.05 to 1.5 wt % of Ti, or from 0.05 to 1 wt % of Ti, orfrom 0.10 to 0.5 wt % of Ti, or from 0.10 to 0.25 wt % of Ti based onthe combined weight of the phosphinimine catalyst, the inert support andthe cocatalyst.

The phosphinimine based (olefin) polymerization catalyst may be fed to areactor system in a number of ways. The polymerization catalyst may befed to a reactor in dry mode using a dry catalyst feeder, examples ofwhich are well known in the art. Alternatively, the polymerizationcatalyst may be fed to a reactor as a slurry in a suitable diluent.Suitable solvents or diluents are inert hydrocarbons well known topersons skilled in the art and generally include aromatics, paraffins,and cycloparaffinics such as for example benzene, toluene, xylene,cyclohexane, fuel oil, isobutane, mineral oil, kerosene and the like.Further specific examples include but are not limited to hexane,heptanes, isopentane and mixtures thereof. Solvents which will notextract appreciable amounts of the phosphinimine catalyst, thecocatalyst or the catalyst modifier away from the inert support arepreferred. The (olefin) polymerization catalyst components, whichinclude at least one phosphinimine catalyst, at least one support, atleast one cocatalyst, and at least one catalyst modifier, may becombined offline and prior to their addition to a polymerization zone,or they may be combined on route to a polymerization zone.

The Polymerization Process

Olefin polymerization processes which are compatible with the currentinvention include gas phase and slurry phase polymerization processes,with gas phase processes being preferred. Preferably, ethylenecopolymerization with an alpha-olefin is carried out in the gas phase,in for example a fluidized bed reactor.

Detailed descriptions of slurry polymerization processes are widelyreported in the patent literature. For example, particle formpolymerization, or a slurry process where the temperature is kept belowthe temperature at which the polymer goes into solution is described inU.S. Pat. No. 3,248,179. Slurry processes include those employing a loopreactor and those utilizing a single stirred reactor or a plurality ofstirred reactors in series, parallel, or combinations thereof.Non-limiting examples of slurry processes include continuous loop orstirred tank processes. Further examples of slurry processes aredescribed in U.S. Pat. No. 4,613,484.

Slurry processes are conducted in the presence of a hydrocarbon diluentsuch as an alkane (including isoalkanes), an aromatic or a cycloalkane.The diluent may also be the alpha olefin comonomer used incopolymerizations. Alkane diluents include propane, butanes, (i.e.,normal butane and/or isobutane), pentanes, hexanes, heptanes andoctanes. The monomers may be soluble in (or miscible with) the diluent,but the polymer is not (under polymerization conditions). Thepolymerization temperature is preferably from about 5° C. to about 200°C., most preferably less than about 120° C. typically from about 10° C.to 100° C. The reaction temperature is selected so that an ethylenecopolymer is produced in the form of solid particles. The reactionpressure is influenced by the choice of diluent and reactiontemperature. For example, pressures may range from 15 to 45 atmospheres(about 220 to 660 psi or about 1500 to about 4600 kPa) when isobutane isused as diluent (see, for example, U.S. Pat. No. 4,325,849) toapproximately twice that (i.e., from 30 to 90 atmospheres—about 440 to1300 psi or about 3000-9100 kPa) when propane is used (see U.S. Pat. No.5,684,097). The pressure in a slurry process must be kept sufficientlyhigh to keep at least part of the ethylene monomer in the liquid phase.The reaction typically takes place in a jacketed closed loop reactorhaving an internal stirrer (e.g., an impeller) and at least one settlingleg. Catalyst, monomers and diluents are fed to the reactor as liquidsor suspensions. The slurry circulates through the reactor and the jacketis used to control the temperature of the reactor. Through a series oflet down valves the slurry enters a settling leg and then is let down inpressure to flash the diluent and unreacted monomers and recover thepolymer generally in a cyclone. The diluent and unreacted monomers arerecovered and recycled back to the reactor.

A gas phase process is commonly carried out in a fluidized bed reactor.Such gas phase processes are widely described in the literature (see,for example, U.S. Pat. Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036;5,352,749; 5,405,922; 5,436,304; 5,433,471; 5,462,999; 5,616,661 and5,668,228). In general, a fluidized bed gas phase polymerization reactoremploys a “bed” of polymer and catalyst which is fluidized by a flow ofmonomer and other optional components which are at least partiallygaseous. Heat is generated by the enthalpy of polymerization of themonomer (and optional comonomer(s)) flowing through the bed. Un-reactedmonomer and other optional gaseous components exit the fluidized bed andare contacted with a cooling system to remove this heat. The cooled gasstream, including monomer, and optional other components (such ascondensable liquids), is then re-circulated through the polymerizationzone, together with “make-up” monomer to replace that which waspolymerized on the previous pass. Simultaneously, polymer product iswithdrawn from the reactor. As will be appreciated by those skilled inthe art, the “fluidized” nature of the polymerization bed helps toevenly distribute/mix the heat of reaction and thereby minimize theformation of localized temperature gradients.

The reactor pressure in a gas phase process may vary from aboutatmospheric to about 600 Psig. In another embodiment, the pressure canrange from about 100 psig (690 kPa) to about 500 psig (3448 kPa). In yetanother embodiment, the pressure can range from about 200 psig (1379kPa) to about 400 psig (2759 kPa). In still another embodiment, thepressure can range from about 250 psig (1724 kPa) to about 350 psig(2414 kPa).

The reactor temperature in a gas phase process may vary according to theheat of polymerization as described above. In a specific embodiment, thereactor temperature can be from about 30° C. to about 130° C. In anotherspecific embodiment, the reactor temperature can be from about 60° C. toabout 120° C. In yet another specific embodiment, the reactortemperature can be from about 70° C. to about 110° C. In still yetanother specific embodiment, the temperature of a gas phase process canbe from about 70° C. to about 100° C.

The fluidized bed process described above is well adapted for thepreparation of polyethylene and polyethylene copolymers. Hence, monomersand comonomers include ethylene and C₃₋₁₂ alpha olefins which areunsubstituted or substituted by up to two C₁₋₆ hydrocarbyl radicals;C₈₋₁₂ vinyl aromatic olefins which are unsubstituted or substituted byup to two substituents selected from C₁₋₄ hydrocarbyl radicals; andC₄₋₁₂ straight chained or cyclic diolefins which are unsubstituted orsubstituted by a C₁₋₄ hydrocarbyl radical. Illustrative non-limitingexamples of alpha-olefins that may be copolymerized with ethyleneinclude one or more of propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene, styrene, alphamethyl styrene, p-t-butyl styrene, and the constrained-ring cyclicolefins such as cyclobutene, cyclopentene, dicyclopentadiene,norbornene, hydrocarbyl-substituted norbornenes, alkenyl-substitutednorbornenes and the like (e.g., 5-methylene-2-norbornene and5-ethylidene-2-norbornene, bicyclo-(2,2,1)-hepta-2,5-diene).

In an embodiment, the invention is directed toward a polymerizationprocess involving the polymerization of one or more of the monomer(s)and comonomer(s) including ethylene alone or in combination with one ormore linear or branched comonomer(s) having from 3 to 30 carbon atoms,preferably 3-12 carbon atoms, more preferably 4 to 8 carbon atoms. Theprocess is particularly well suited to copolymerization reactionsinvolving polymerization of ethylene in combination with one or more ofthe comonomers, for example, the alpha-olefins: propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, styrene andcyclic and polycyclic olefins such as cyclopentene, norbornene andcyclohexene or a combination thereof. Other comonomers for use withethylene can include polar vinyl monomers, diolefins such as1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene,norbornadiene, and other unsaturated monomers including acetylene andaldehyde monomers. Higher alpha-olefins and polyenes or macromers can beused also. In some embodiments the comonomer is an alpha-olefin havingfrom 3 to 15 carbon atoms, for example 4 to 12 carbon atoms, or forexample 4 to 10 carbon atoms.

In an embodiment of the present invention, ethylene is copolymerizedwith an alpha olefin having from 3-10 carbon atoms and ethylene makes upat least 75 wt % of the total olefin feed entering the reactor.

In an embodiment of the present invention, ethylene is copolymerizedwith an alpha olefin having from 3-10 carbon atoms and ethylene makes upat least 85 wt % of the total olefin feed entering the reactor.

In embodiments of the present invention, ethylene is copolymerized withpropylene, 1-butene, 1-hexene or 1-octene.

In an embodiment of the present invention, ethylene is copolymerizedwith 1-butene and ethylene makes up at least 75 weight % (i.e., wt %) ofthe total olefin feed entering the reactor.

In an embodiment of the present invention, ethylene is copolymerizedwith 1-hexene and ethylene makes up at least 75 wt % of the total olefinfeed entering the reactor.

In an embodiment of the present invention, ethylene is copolymerizedwith 1-hexene and ethylene makes up at least 85 wt % of the total olefinfeed entering the reactor.

Gas phase fluidized bed polymerization processes may employ a polymerseed bed in the reactor prior to initiating the polymerization process.It is contemplated by the current invention to use a polymer seed bedthat has been treated with a catalyst modifier or an optional scavenger(see below). In addition, the polymer products obtained by using thecatalysts and processes of the current invention may themselves be usedas polymer seed bed materials.

Optional Scavenger

Optionally, scavengers are added to the polymerization process. Thepresent invention can be carried out in the presence of any suitablescavenger or scavengers. Scavengers are well known in the art.

In an embodiment of the invention, scavengers are organoaluminumcompounds having the formula: Al³(X³)_(n)(X⁴)_(3-n), where (X³) is ahydrocarbyl having from 1 to about 20 carbon atoms; (X⁴) is selectedfrom alkoxide or aryloxide, any one of which having from 1 to about 20carbon atoms; halide; or hydride; and n is a number from 1 to 3,inclusive; or hydrocarbyl aluminoxanes having the formula:R³ ₂Al¹O(R³Al¹O)_(m)Al¹R³ ₂

wherein each R³ is independently selected from C₁₋₂₀ hydrocarbylradicals and m is from 3 to 50. Some non-limiting preferred scavengersuseful in the current invention include triisobutylaluminum,triethylaluminum, trimethylaluminum or other trihydrocarbyl aluminumcompounds.

The scavenger may be used in any suitable amount but by way ofnon-limiting examples only, can be present in an amount to provide amolar ratio of Al:M (where M is the metal of the phosphinimine catalyst)of from about 20 to about 2000, or from about 50 to about 1000, or fromabout 100 to about 500. Generally the scavenger is added to the reactorprior to the polymerization catalyst and in the absence of additionalpoisons and over time declines to 0, or is added continuously.

Optionally, the scavengers may be independently supported. For example,an inorganic oxide that has been treated with an organoaluminum compoundor hydrocarbyl aluminoxane may be added to the polymerization reactor.The method of addition of the organoaluminum or hydrocarbyl aluminoxanecompounds to the support is not specifically defined and is carried outby procedures well known in the art.

A scavenger may optionally be added to the catalyst modifier prior toinclusion of the catalyst modifier in a polymerization catalyst or priorto the combination of a catalyst modifier with another polymerizationcatalyst component (i.e. one or more of the phosphinimine catalyst, theinert support, or the cocatalyst).

Polymer

The polymer compositions made using the present invention are mostpreferably copolymers of ethylene and an alpha olefin selected from1-butene, 1-hexene and 1-octene.

In embodiments of the invention, the copolymer composition will compriseat least 75 weight % of ethylene units, or at least 80 wt % of ethyleneunits, or at least 85 wt % of ethylene units with the balance being analpha-olefin unit, based on the weight of the copolymer composition.

Polymer properties such as average molecular weight (e.g. Mw, Mn andMz), molecular weight distribution (i.e., Mw/Mn), density, melt indices(e.g. I₂, I₅, I₂₁, I₁₀), melt index or melt flow ratios (e.g., I₂₁/I₂,I₂₁/I₅), composition distribution breadth index (CDBI), TREF-profile,comonomer distribution profile, and the like as these terms are definedfurther below and in for example co-pending CA Application No. 2,734,167(to the same Applicant) are not specifically defined. By way ofnon-limiting example only, a polymer composition which may be made usingthe present invention, may have a density of from 0.910 g/cc to 0.93g/cc, a melt index of from 0.5 to 10.0 g/10 min, a melt flow ratio(I₂₁/I₂) of from 14 to 18, a weight average molecular weight of from40,000 to 140,000, and a unimodal or bimodal TREF profile.

Catalyst Modifier Addition

In some embodiments, the catalyst modifier affects at least one of thefollowing: reactor static level, catalyst static level, reactortemperature control, catalyst productivity, copolymer compositiondistribution, and film gel count.

Use of a specific amount of the catalyst modifier (e.g., from about 0.5to about 4.0 wt % based on the weight of the polymerization catalyst)may actually improve the catalyst productivity as is further taughtbelow.

In some embodiments, the catalyst modifier may be included in thepolymerization catalyst at any point during the preparation of thepolymerization catalyst so long as the catalyst modifier is added beforethe polymerization catalyst enters a polymerization zone orpolymerization reactor. Hence, in an embodiment of the invention, atleast one phosphinimine catalyst, at least one inert support, at leastone cocatalyst and at least one catalyst modifier are combined in anyorder prior to or on route to their entry into a polymerization zone orreactor. In specific embodiments of the invention: the catalyst modifiermay be added to a support after both the phosphinimine catalyst and thecocatalyst have been added; the catalyst modifier may be added to asupport before either of the phosphinimine catalyst or the cocatalystare added; the catalyst modifier may be added to a support after thephosphinimine catalyst but before the cocatalyst; the catalyst modifiermay be added to a support after the cocatalyst but before thephosphinimine catalyst. Also, the catalyst modifier can be added inportions during any stage of the preparation of the polymerizationcatalyst.

In an embodiment of the present invention, the catalyst modifier isadded to a “finished” polymerization catalyst already comprising thephosphinimine catalyst, inert support and cocatalyst (as used here, theterm “finished” is meant to denote that the catalyst modifier is not yetpresent in the polymerization catalyst). The catalyst modifier can beadded to the “finished” polymerization catalyst offline and prior toaddition of the polymerization catalyst to the polymerization zone, orthe catalyst modifier may be added to the “finished” polymerizationcatalyst on route to a reactor.

In an embodiment of the present invention, the catalyst modifier isadded to an inert support, prior to the addition of the phosphiniminecatalyst and prior to the addition of the cocatalyst to prepare thepolymerization catalyst.

The catalyst modifier may be included in the polymerization catalyst (orwhere appropriate, added to a polymerization catalyst component orcomponents which comprise at least one of the phosphinimine catalyst,the inert support and the cocatalyst) in any suitable manner. By way ofnon-limiting example, the catalyst modifier may be dry blended (if it isa solid) with a “finished” polymerization catalyst (or a polymerizationcatalyst component) or it may be added neat (if the catalyst modifier isa liquid) or it may be added as solution or slurry in a suitablehydrocarbon solvent or diluent respectively. The “finished”polymerization catalyst (or polymerization catalyst components) canlikewise be put into solution or made into a slurry using suitablesolvents or diluents respectively, followed by addition of the catalystmodifier (as a neat solid or liquid or as a solution or a slurry insuitable solvents or diluents) or vice versa. Alternatively, thecatalyst modifier may be deposited onto a separate support and theresulting supported catalyst modifier blended either dry or in a slurrywith the “finished” polymerization catalyst, but this method is notpreferred. The catalyst modifier can be combined neat (if a liquid) oras a solution or slurry in a suitable hydrocarbon solvent or diluentwith an inert support prior to the addition of a phosphinimine catalystand/or a cocatalyst. The catalyst modifier may also be dry blended (ifit is a solid) with an inert support prior to addition of thephosphinimine catalyst and/or the cocatalyst.

Suitable solvents or diluents are inert hydrocarbons and include but arenot limited to aromatics, paraffins, and cycloparaffinics such as forexample benzene, toluene, xylene, cyclohexane, fuel oil, isobutane,mineral oil, kerosene and the like. Further specific examples includebut are not limited to hexane, heptanes, isopentane, cyclohexane,toluene and mixtures thereof.

Removal of diluents or solvents to give the polymerization catalyst as asolid or powder can be carried out using any suitable means known in theart. For example, the catalyst may be isolated by one or more filtrationor decantation steps, or one or more evaporation steps. Removal ofdiluents or solvents by evaporation/drying is well known, but theevaporation may be carried out under conditions which do not adverselyaffect the performance of the polymerization catalyst. Removal ofsolvent or diluents can be carried out under ambient pressures orreduced pressures. Removal of diluents or solvents can be achieved underambient temperatures or elevated temperatures, provided that elevatedtemperatures do not lead to catalyst deactivation. Diluents or solventsmay in some circumstances (i.e., for low boiling diluents/solvents) be“blown off” using an inert gas. The time required to remove the diluentsor solvents is not specifically defined.

Polymerization catalysts in the form of a solid can be fed to apolymerization zone using well known solid catalyst feeder equipment.Alternatively, the polymerization catalyst may be used in slurried form.By “slurried form” it is meant that the polymerization catalyst issuspended in a suitable diluent or mixture of diluents. Suitablediluents may include but are not limited to cyclohexane, pentane,heptanes, isopentane, mineral oil and mixtures thereof. The diluentchosen may be one in which little or no extraction of polymerizationcatalyst components from the support occurs. Such a slurry form catalystcan be fed to a polymerization reactor zone using suitable slurry feedequipment which is well known in the art.

In an embodiment, the amount of catalyst modifier added to a reactor (orother associated process equipment) is conveniently represented hereinas the parts per million (ppm) of catalyst modifier based on the weightof copolymer produced.

In an embodiment, the amount of catalyst modifier included in apolymerization catalyst is conveniently represented herein as a weightpercent (wt %) of the catalyst modifier based on the combined weight ofthe phosphinimine catalyst, the inert support and the cocatalyst. Inorder to avoid any ambiguity, the phrase “weight of the polymerizationcatalyst” includes the weight of the phosphinimine catalyst, the inertsupport, and the cocatalyst but not the weight of the catalyst modifier.

The total amount of catalyst modifier included in the polymerizationcatalyst can range from about 0.1 to 10 weight percent (or smallerranges within this range) based on the combined weight of thephosphinimine catalyst, the inert support and the cocatalyst. However,to maximize catalyst productivity and reactor operability at the sametime, the amount of catalyst modifier included in the polymerizationcatalyst is preferably from 0.25 to 6.0 weight percent (i.e., wt % basedon the weight of the phosphinimine catalyst, the inert support and thecocatalyst), or from 0.25 to 5.0 weight percent, or from 0.5 to 4.5weight percent, or from 1.0 to 4.5 weight percent, or from 0.75 to 4.0weight percent, or from 0.5 to 4.0 weight percent, or from 0.25 to 4.0weight percent, or from 1.0 to 4.0 weight percent, or from 0.5 to 3.5weight percent, or from 1.25 to 3.75 weight percent, or from 1.0 to 3.5weight percent, or from 1.5 to 3.5 weight percent, or from 0.75 to 3.75weight percent, or from 0.25 to 3.75 weight percent, or from 0.75 to 3.5weight percent, or from 1.0 to 3.75 weight percent.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifiercomprises a “long chain amine” compound as described above in “TheCatalyst Modifier” section and which is present in from 0.25 to 6.0weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.25 to 6.0 weight percent based on the weight of i),ii) and iii) of the polymerization catalyst and comprises a compoundhaving the formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is ahydrocarbyl group having from 5 to 30 carbon atoms, R² is hydrogen or ahydrocarbyl group having from 1 to 30 carbon atoms, x is 1 or 0; when xis 1, y is 1 and n is an integer from 1 to 30; when x is 0, y is 2 andeach n is independently an integer from 1 to 30.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.25 to 5.0 weight percent based on the weight of i),ii) and iii) of the polymerization catalyst and comprises a compoundhaving the formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is ahydrocarbyl group having from 5 to 30 carbon atoms, R² is hydrogen or ahydrocarbyl group having from 1 to 30 carbon atoms, x is 1 or 0; when xis 1, y is 1 and n is an integer from 1 to 30; when x is 0, y is 2 andeach n is independently an integer from 1 to 30.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.5 to 4.5 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and nis an integer from 1 to 30; when x is 0, y is 2 and each n isindependently an integer from 1 to 30.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 1.0 to 4.0 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and nis an integer from 1 to 30; when x is 0, y is 2 and each n isindependently an integer from 1 to 30.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 1.0 to 4.0 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises at least onecompound represented by the formula: R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) whereR¹ is a hydrocarbyl group having from 5 to 30 carbon atoms, and n and mare integers from 1 to 20.

In an embodiment of the invention, the polymerization catalystcomprises: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 1.0 to 4.0 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises at least onecompound represented by the formula: R¹N((CH₂)_(n)OH)₂ where R¹ is ahydrocarbyl group having from 6 to 30 carbon atoms, and each n isindependently an integer from 1-20.

One measure of reactor operability is the level of static present in oneor more locations in a gas phase fluidized bed polymerization system.The level of static present in the polymerization catalyst is also auseful proxy for potential reactor operability problems. The effect ofthe catalyst modifier on static may be conveniently monitored with oneor more static probes. Static probes are designed to register staticactivity above or below zero. In a gas phase polymerization run, afouling event is sometimes preceded by large non-zero measurements ofstatic. One or more static probes can be used to measure the level ofstatic anywhere in the reactor proper (including upper, lower orintermediate bed probes), at a location within the entrainment zone, ata location within the recycle stream, at the distributor plate, at theannular disk which provides access to the flowing stream of gas enteringthe reactor, and the like as discussed in U.S. Patent Application No.2005/0148742A1, which is incorporated herein by reference. Hence, thestatic probes themselves may be designated as at least one recycle lineprobe, at least one annular disk probe, at least one distributor plateprobe, at least one upper reactor static probe, an annular disk probe ora conventional probe which is located within the fluidized bed. Thepolymerization catalyst static can be measured using a static probelocated in the catalyst injection tube, or catalyst metering device.

In a conventional reactor wall static probe, the probe measures theelectric current that flows from a probe tip and which results fromparticle impact therewith. The particles could be resin particles orcatalyst particles for example. The probe measures current per unit ofarea on the probe tip which serves as an estimate of the charge transferoccurring on the reactor wall. In this scenario, the probe tip is meantto simulate a small portion of the reactor wall. The probe tip may bemade of any suitable conducting materials such as carbon steel, iron,stainless steel, titanium, platinum, nickel, Monel®, copper, aluminumand the like as further described in U.S. Pat. No. 6,008,662, which isincorporated herein by reference.

More generally, static probes include a metallic probe tip, one or moresignal wires, and an electric feed to a measuring instrument asdiscussed in U.S. Patent Application No. 2005/0148742 A1. Any instrumentor device capable of measuring current flow from the probe tip to groundcan be used. These include for example an ammeter, a picoammeter, amulti-meter, or electrometer. The current may also be measured in anindirect way by instead determining the voltage generated by the currentwhen it is passed through an in-series resistor. The current can bedetermined from voltage using Ohm's law as further described in U.S.Pat. No. 6,008,662, which is incorporated herein by reference.

Typical current levels measured with a conventional reactor wall staticprobe range from ±0.1 to 10 nanoamps/cm², or smaller ranges within thisrange (e.g., ±0.1 to 8 nanoamps/cm², ±0.1 to 6 nanoamps/cm² and thelike). The measurements of current will generally be represented asaverages over a given time period or they may be represented as the rootmean squared values in order to provide all positive number values.

Any one or more static probes in any location in the fluidized bedsystem may be determinative of the onset of a reactor discontinuityevent.

The effect of the catalyst modifier on reactor operability may also beevidenced by other observations not limited to that of the measurementof static activity. For example, productivity levels can be measured (ingrams of polymer produced per gram of catalyst used) as an indicator ofoverall reactor and catalyst performance. Activity measurements may besimilarly used (by incorporating a time dimension into productivitymeasurements). Direct or indirect observations of temperaturefluctuations at various locations in a fluidized bed reactor system (orother reactor systems) can also be monitored and the ideal amount ofcatalyst modifier determined in order to minimize heat fluctuations.Common thermocouples can be used at various locations for this purpose.

In an embodiment of the invention, the polymerization process is carriedout by introducing a polymerization catalyst into a reactor, thepolymerization catalyst comprising: i) a phosphinimine catalyst; ii) aninert support; iii) a cocatalyst; and iv) a catalyst modifier; whereinthe catalyst modifier comprises a “long chain amine” compound asdescribed above in “The Catalyst Modifier” section and which is presentin from 0.25 to 6.0 weight percent based on the weight of i), ii) andiii) of the polymerization catalyst.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 0.25to 6.0 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and n is aninteger from 1 to 30; when x is 0, y is 2 and each n is independently aninteger from 1 to 30.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 0.25to 5.0 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and n is aninteger from 1 to 30; when x is 0, y is 2 and each n is independently aninteger from 1 to 30.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 0.5to 4.5 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and n is aninteger from 1 to 30; when x is 0, y is 2 and each n is independently aninteger from 1 to 30.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 1.0to 4.0 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and n is aninteger from 1 to 30; when x is 0, y is 2 and each n is independently aninteger from 1 to 30.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 1.25to 3.75 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and n is aninteger from 1 to 30; when x is 0, y is 2 and each n is independently aninteger from 1 to 30.

In an embodiment of the invention, the polymerization process is carriedout in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; iii) a cocatalyst; and iv)a catalyst modifier; wherein the catalyst modifier is present from 1.5to 3.5 weight percent based on the weight of i), ii) and iii) of thepolymerization catalyst and comprises a compound having the formula:R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and n is aninteger from 1 to 30; when x is 0, y is 2 and each n is independently aninteger from 1 to 30.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; improves at least one ofreactor static level (i.e., decreases), catalyst static level (i.e.,decreases), reactor temperature excursions (i.e., decreases) andcatalyst productivity (i.e., increases), relative to a gas phasepolymerization process carried out in a reactor in the presence of apolymerization catalyst comprising: i) a phosphinimine catalyst; ii) aninert support; and iii) a cocatalyst, but no catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier, wherein the catalyst modifieris present from 0.5 to 4.5 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst; improves at least one ofreactor static level (i.e., decreases), catalyst static level (i.e.,decreases), reactor temperature excursions (i.e., decreases) andcatalyst productivity (i.e., increases), relative to a gas phasepolymerization process carried out in a reactor in the presence of apolymerization catalyst comprising: i) a phosphinimine catalyst; ii) aninert support; and iii) a cocatalyst, but no catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.5 to 4.5 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and nis an integer from 1 to 30; when x is 0, y is 2 and each n isindependently an integer from 1 to 30; decreases the reactor staticlevel relative to a gas phase polymerization process carried out in areactor in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; and iii) a cocatalyst, butno catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.5 to 4.5 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and nis an integer from 1 to 30; when x is 0, y is 2 and each n isindependently an integer from 1 to 30; decreases the catalyst staticlevel relative to a gas phase polymerization process carried out in areactor in the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; and iii) a cocatalyst, butno catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 0.5 to 4.5 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and nis an integer from 1 to 30; when x is 0, y is 2 and each n isindependently an integer from 1 to 30; decreases the severity of reactortemperature excursions relative to a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; and iii)a cocatalyst, but no catalyst modifier.

In an embodiment of the invention, a gas phase polymerization processcarried out in a reactor in the presence of a polymerization catalystcomprising: i) a phosphinimine catalyst; ii) an inert support; iii) acocatalyst; and iv) a catalyst modifier; wherein the catalyst modifieris present from 1.0 to 4.0 weight percent based on the weight of i), ii)and iii) of the polymerization catalyst and comprises a compound havingthe formula: R¹R² _(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R² is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and nis an integer from 1 to 30; when x is 0, y is 2 and each n isindependently an integer from 1 to 30; has increased productivityrelative to a gas phase polymerization process carried out in a reactorin the presence of a polymerization catalyst comprising: i) aphosphinimine catalyst; ii) an inert support; and iii) a cocatalyst, butno catalyst modifier.

The presence of a catalyst modifier in the polymerization catalyst mayalso affect the properties of ethylene copolymers produced during gasphase polymerization of ethylene and an alpha-olefin as well as theproperties of films made with those copolymers.

For example, the catalyst modifier may, when added in appropriateamounts to a phosphinimine based polymerization catalyst, alter thecomposition distribution (as defined below) in an ethylene copolymerrelative to copolymer produced with a phosphinimine based polymerizationcatalyst not treated with the catalyst modifier. The catalyst modifiermay, when added in appropriate amounts to a phosphinimine basedpolymerization catalyst, increase the short chain branching homogeneityof an ethylene copolymer relative to copolymer produced with aphosphinimine based polymerization catalyst not treated with a catalystmodifier. More specifically, a catalyst modifier may, when present inthe polymerization catalyst in appropriate amounts, alter one or more ofthe following: the composition distribution breadth index (CDBI) of theethylene copolymer as measured using temperature rising elutionfractionation (TREF) methods; the weight percent of a higher temperatureeluting material (i.e., from 90° C. to 105° C.) observed in TREF profileobtained for the ethylene copolymer; and the comonomer distributionprofile in the ethylene copolymer as measured by gel permeationchromatography with Fourier transform infra-red detection (GPC-FTIR).

Ethylene copolymers can be defined by a composition distribution breadthindex (CDBI), which is a measure as to how comonomers are distributed inan ethylene copolymer. The definition of composition distributionbreadth index (CDBI) can be found in U.S. Pat. No. 5,206,075 and PCTpublication WO 93/03093. The CDBI is conveniently determined usingtechniques which isolate polymer fractions based on their solubility(and hence their comonomer content). For example, temperature risingelution fractionation (TREF) as described by Wild et al. J. Poly. Sci.,Poly. Phys. Ed. Vol. 20, p 441, 1982 can be employed. From the weightfraction versus composition distribution curve, the CDBI is determinedby establishing the weight percentage of a copolymer sample that has acomonomer content within 50% of the median comonomer content on eachside of the median. Generally, ethylene copolymers with a CDBI of lessthan about 50%, are considered “heterogeneously branched” copolymerswith respect to the short chain branching. Such heterogeneously branchedmaterials may include a highly branched fraction, a medium branchedfraction and a higher density fraction having little or no short chainbranching. In contrast, ethylene copolymers with a CDBI of greater thanabout 50% are considered “homogeneously branched” copolymers withrespect to short chain branching in which the majority of polymer chainsmay have a similar degree of branching.

In embodiments of the invention, an ethylene copolymer made with apolymerization catalyst comprising: i) a phosphinimine catalyst, ii) aninert support, iii) a cocatalyst and iv) from 1.0 to 4.0 wt % of acatalyst modifier (based on the weight of i), ii), and iii) of thepolymerization catalyst); has an at least 3%, or at least 5%, or atleast 7% higher composition distribution breadth index (as measured byTREF) than an ethylene copolymer made with a catalyst comprising: i) aphosphinimine catalyst, ii) an inert support, and iii) a cocatalyst, butno catalyst modifier.

An ethylene copolymer can be defined by a weight percent of a highertemperature eluting material (i.e., from 90° C. to 105° C.) observed inTREF profile. The amount of copolymer which elutes at a temperature offrom 90° C. to 105° C. is another indication as to how comonomers aredistributed in an ethylene copolymer.

In embodiments of the invention, an ethylene copolymer made with apolymerization catalyst comprising i) a phosphinimine catalyst, ii) aninert support, iii) a cocatalyst and iv) from 1.0 to 4.0 wt % of acatalyst modifier (based on the weight of i), ii) and iii) of thepolymerization catalyst) has a weight percent of an ethylene copolymerfraction (based on the weight of the copolymer) which elutes at from 90°C. to 105° C. in a TREF analysis which is decreased by at least 1%, orby at least 2%, or by at least 3% relative to an ethylene copolymer madewith a catalyst comprising: i) a phosphinimine catalyst, ii) an inertsupport, and iii) a cocatalyst, but no catalyst modifier.

Ethylene copolymers can have a number of different comonomerdistribution profiles which represent how the comonomers are distributedamongst polymer chains of different molecular weight. The so called“comonomer distribution profile” is most typically measured usingGel-Permeation Chromatography with Fourier Transform Infra-Red detection(GPC-FTIR). If the comonomer incorporation decreases with molecularweight, as measured using GPC-FTIR, the distribution is described as“normal” or “negative”. If the comonomer incorporation is approximatelyconstant with molecular weight, as measured using GPC-FTIR, thecomonomer distribution is described as “flat”. The terms “reversedcomonomer distribution” and “partially reversed comonomer distribution”mean that in the GPC-FTIR data obtained for the copolymer, there is oneor more higher molecular weight components having a higher comonomerincorporation than in one or more lower molecular weight segments. Ifthe comonomer incorporation rises with molecular weight, thedistribution is described as “reversed”. Where the comonomerincorporation rises with increasing molecular weight and then declines,the comonomer distribution is described as “partially reversed”.

In embodiments of the invention, use of a polymerization catalystcomprising i) a phosphinimine catalyst, ii) an inert support, iii) acocatalyst, and iv) from 1.0 to 4.0 wt % of a catalyst modifier (basedon the weight of i), ii) and iii) of the polymerization catalyst) forethylene/alpha-olefin copolymerization, changes the comonomerdistribution profile of an ethylene copolymer from a normal profile to aflat profile, or from a flat profile to a reversed profile or from anormal profile to a reversed profile, or from a reversed profile to amore reversed profile, relative to an ethylene copolymer made with apolymerization catalyst comprising: i) a phosphinimine catalyst, ii) aninert support, and iii) a cocatalyst, but no catalyst modifier.

The catalyst modifier, may when included in the phosphinimine basedpolymerization catalyst in appropriate amounts, provide ethylenecopolymer which when cast into film has reduced numbers of gels,relative to copolymer produced with a phosphinimine based olefinpolymerization catalyst not treated with a catalyst modifier.

In an embodiment of the invention, the presence of from 1.0 to 4.0weight percent of a catalyst modifier in a polymerization catalystcomprising i) a phosphinimine catalyst, ii) an inert support, iii) acocatalyst, and iv) a catalyst modifier decreases the number of gelspresent (by OCS gel count) in a film cast from a copolymer obtainedusing the polymerization catalyst (relative to film cast from acopolymer obtained using a polymerization catalyst not treated with acatalyst modifier).

In embodiments of the invention, the presence of from 1.0 to 4.0 weightpercent of a catalyst modifier in an olefin polymerization catalystcomprising i) a phosphinimine catalyst, ii) an inert support, iii) acocatalyst, and iv) a catalyst modifier, decreases the number of gelspresent in a film cast from a copolymer obtained using the olefinpolymerization catalyst, from above 100 to below 10, or from above 50 tobelow 10, or from above 20 to below 10 according to OCS gel count.

Although a catalyst modifier, must in the present invention, be presentin the polymerization catalyst at some point before adding thepolymerization catalyst to a polymerization zone, the present inventiondoes not preclude embodiments in which a catalyst modifier is also addeddirectly to a reaction zone (e.g., the reactor per se, such as a gasphase reactor) or to some other part of a gas phase process which isassociated with the reaction zone (collectively “the reactor system”).

When not added as a polymerization catalyst component as describedabove, the type of catalyst modifier which can be used in the presentinvention is not specifically defined and includes the long chainsubstituted amine catalyst modifiers described above, as well any ofthose recognized in the prior art to be usefully applied in gas-phasepolymerization. Catalyst modifiers are also recognized in the art by theterm “continuity additive” or “antistatics” or “anti-static agents”.Other catalyst modifiers which may be fed to a reactor system in thepresent invention include compounds such as carboxylate metal salts (seeU.S. Pat. Nos. 7,354,880; 6,300,436; 6,306,984; 6,391,819; 6,472,342 and6,608,153 for examples), polysulfones, polymeric polyamines and sulfonicacids (see U.S. Pat. Nos. 6,562,924; 6,022,935 and 5,283,278 forexamples). Polyoxyethylenealkylamines, which are described in, forexample, in European Patent Application No. 107,127, may also be fed toa reactor system. Still further catalyst modifiers that may be fed to areactor system include aluminum stearate and aluminum oleate. Somecatalyst modifiers that may be fed to a reactor system are suppliedcommercially under the trademarks OCTASTAT™ and STADIS™. The catalystmodifier STADIS, which is described in U.S. Pat. Nos. 7,476,715;6,562,924 and 5,026,795 and is available from Octel Starreon, may alsobe fed to a reactor system. STADIS generally comprises a polysulfonecopolymer, a polymeric amine and an oil soluble sulfonic acid.

The catalyst modifier may be fed to a reactor system using anyappropriate method known to persons skilled in the art. For example, thecatalyst modifier may be fed to a reactor system as a neat solid orliquid or as a solution or as a slurry in a suitable solvent or diluentrespectively. Suitable solvents or diluents are inert hydrocarbons wellknown to persons skilled in the art and generally include aromatics,paraffins, and cycloparaffinics such as for example benzene, toluene,xylene, cyclohexane, fuel oil, isobutane, mineral oil, kerosene and thelike. Further specific examples include but are not limited to hexane,heptanes, isopentane and mixtures thereof. Alternatively, the catalystmodifier may be added to an inert support material and then fed to apolymerization reactor as a dry feed or a slurry feed. The catalystmodifier may be fed to various locations in a reactor system. Whenconsidering a fluidized bed process for example, the catalyst modifiermay be fed directly to any area of the reaction zone (e.g., the reactorper se), or any area of the entrainment zone, or it may be fed to anyarea within the recycle loop, where such areas are found to be effectivesites at which to feed a catalyst modifier. For example, furthercatalyst modifier can be added to a reactor with all or a portion of oneor more of the monomers or the cycle gas; or further catalyst modifiercan be added through a dedicated feed line or added to any convenientfeed stream including an ethylene feed stream, a comonomer feed stream,a catalyst feed line or a recycle line; or further catalyst modifier canbe fed to a location in a fluidized bed system in a continuous orintermittent manner; or further catalyst modifier can be added to areactor at a time before, after or during the start of thepolymerization reaction; or further catalyst modifier can be added byspraying a solution or mixture of the catalyst modifier directly into areaction zone; or further catalyst modifier can be added to a polymerseed bed present in a reactor prior to starting the polymerizationreaction by introduction of the polymerization catalyst.

When further catalyst modifier is desired then it may be added as asolution or mixture with a solvent or diluent respectively, and thecatalyst modifier may make up for example from 0.1 to 30 wt % of thesolution or mixture, or from 0.1 to 20 wt %, or from 0.1 to 10 wt %, orfrom 0.1 to 5 wt % or from 0.1 to 2.5 wt % or from 0.2 to 2.0 wt %,although a person skilled in the art will recognize that further,possibly broader ranges, may also be used and so the invention shouldnot be limited in this regard.

When further catalyst modifier is desired then the amount of catalystmodifier fed to a reactor or reactor system will generally not exceedabout 150 ppm, or 100 ppm, or 75 ppm, or 50 ppm, or 25 ppm (parts permillion based on the weight of the (co)polymer being produced).

Hence, in embodiments of the invention, the catalyst modifier fed to areaction zone or to some other part of a gas phase process which isassociated with the reaction zone will be from 150 to 0 ppm, andincluding narrower ranges within this range, such as but not limited to,from 150 to 1 ppm, or from 150 to 5 ppm, or from 100 to 0 ppm, or from100 to 1 ppm, or from 100 to 5 ppm, or from 75 to 0 ppm, or from 75 to 1ppm, or from 75 to 5 ppm, or from 50 to 0 ppm, or from 50 to 1 ppm, orfrom 50 to 5 ppm, or from 25 to 0 ppm, or from 25 to 1 ppm, or from 25to 5 ppm (parts per million by weight of the polymer being produced).

In an embodiment of the invention, the catalyst modifier fed to areaction zone or to some other part of a gas phase process which isassociated with the reaction zone, will be greater than 0 ppm, but ≦50ppm, or ≦40 ppm, or ≦30 ppm, or ≦25 ppm (parts per million by weight ofthe polymer being produced).

In an embodiment of the invention, a catalyst modifier is fed to a gasphase reactor and comprises a compound having the formula: R¹R²_(x)N((CH₂)_(n)OH)_(y) where R¹ is a hydrocarbyl group having from 5 to30 carbon atoms, R² is hydrogen or a hydrocarbyl group having from 1 to30 carbon atoms, x is 1 or 0; when x is 1, y is 1 and n is an integerfrom 1 to 30; when x is 0, y is 2 and each n is independently an integerfrom 1 to 30.

In an embodiment of the invention, a catalyst modifier is fed to a gasphase reactor and comprises at least one compound represented by theformula: R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) where R¹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, and n and m are integers from 1 to 20.

In an embodiment of the invention, a catalyst modifier is fed to a gasphase reactor and comprises at least one compound represented by theformula: R¹N((CH₂)_(n)OH)₂ where R¹ is a hydrocarbyl group having from 6to 30 carbon atoms, and n is independently an integer from 1-20.

In an embodiment of the invention, a catalyst modifier is fed to a gasphase reactor and comprises at least one compound represented by theformula: R¹N((CH₂)_(n)OH)₂ where R¹ is a hydrocarbyl group having from 6to 30 carbon atoms, and n is 2 or 3.

In an embodiment of the invention, a catalyst modifier is fed to a gasphase reactor and comprises at least one compound represented by theformula: R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having from 8 to22 carbon atoms.

In an embodiment of the invention, a catalyst modifier is fed to a gasphase reactor and comprises a compound represented by the formula:C₁₈H₃₇N(CH₂CH₂OH)₂.

In an embodiment of the invention, a catalyst modifier is fed to a gasphase reactor and comprises compounds represented by the formulas:C₁₃H₂₇N(CH₂CH₂OH)₂ and C₁₅H₃₁N(CH₂CH₂OH)₂.

In an embodiment of the invention, a catalyst modifier is fed to a gasphase reactor and comprises a mixture of compounds represented by theformula: R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having from 8 to18 carbon atoms.

The present invention will now be further illustrated by the followingnon-limiting examples.

EXAMPLES Catalyst Modifier

Atmer-163™ was obtained from CRODA CANADA LTD and dried over 3 Åmolecular sieves for several days prior to use. Atmer-163 has as itsmain component, a mixture of C13 to C15 hydrocarbyl diethanolamines,CH₃(CH₂)_(n)N(CH₂CH₂OH)₂ where n is 12 to 14.

Armostat-1800™ was obtained from Akzo Nobel and purified by drying atoluene or pentane solution over 3 Å molecular sieves for several daysprior to use. Armostat-1800 is principally a long chain substitutedalkanolamine having the formula: C₁₈H₃₇N(CH₂CH₂OH)₂.

In an alternative manner of drying the Armostat-1800 material, 950 g ofthe material, was loaded in a 2 L-round bottom flask and melted in anoil bath at 80° C. The oil bath temperature was then raised to 110° C.and a high vacuum was applied while maintaining stirring. Bubbles wereobserved due to the release of gas and moisture vapor. Approximately twohours later, gas evolution subsided and heating/evacuation was continuedfor another hour. The Armostat-1800 material was then cooled down toroom temperature and stored under nitrogen atmosphere until use. Themoisture level in the purified Armostat-1800 was determined to be 110ppm by Karl-Fischer titration method.

Polymerization Catalysts

All reactions involving air and or moisture sensitive compounds wereconducted under nitrogen using standard Schlenk and cannula techniques,or in a glovebox. Reaction solvents were purified either using thesystem described by Pangborn et. al. in Organometallics 1996, v 15, p.1518 or used directly after being stored over activated 4 Å molecularsieves. The aluminoxane used was a 10% MAO solution in toluene suppliedby Albemarle which was used as received. The support used was silicaSylopol 2408 obtained from W.R. Grace. & Co. The support was calcined byfluidizing with air at 200° C. for 2 hours followed by nitrogen at 600°C. for 6 hours and stored under nitrogen. The phosphinimine catalystcompound (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ was made in a mannersimilar to the procedure given in U.S. Pat. No. 7,531,602 (see Example2). The phosphinimine compound (1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ wasmade as follows. To distilled indene (15.0 g, 129 mmol) in heptane (200mL) was added BuLi (82 mL, 131 mmol, 1.6 M in hexanes) at roomtemperature. The resulting reaction mixture was stirred overnight. Themixture was filtered and the filter cake washed with heptane (3×30 mL)to give indenyllithium (15.62 g, 99% yield). Indenyllithium (6.387 g,52.4 mmol) was added as a solid over 5 minutes to a stirred solution ofC₆F₅CH₂—Br (13.65 g, 52.3 mmol) in toluene (100 mL) at room temperature.The reaction mixture was heated to 50° C. and stirred for 4 h. Theproduct mixture was filtered and washed with toluene (3×20 mL). Thecombined filtrates were evaporated to dryness to afford 1-C₆F₅CH₂-indene(13.58 g, 88%). To a stirred slurry of TiCl₄.2THF (1.72 g, 5.15 mmol) intoluene (15 mL) was added solid (t-Bu)₃P═N—Li (1.12 g, 5 mmol) at roomtemperature. The resulting reaction mixture was heated at 100° C. for 30min and then allowed to cool to room temperature. This mixturecontaining ((t-Bu)₃P═N)TiCl₃ (1.85 g, 5 mmol) was used in the nextreaction. To a THF solution (10 mL) of 1-C₆F₅CH₂-indene (1.48 g, 5 mmol)cooled at −78° C. was added n-butyllithium (3.28 mL, 5 mmol, 1.6 M inhexanes) over 10 minutes. The resulting dark orange solution was stirredfor 20 minutes and then transferred via a double-ended needle to atoluene slurry of ((t-Bu)₃P═N)TiCl₃ (1.85 g, 5 mmol). The cooling wasremoved from the reaction mixture which was stirred for a further 30minutes. The solvents were evaporated to afford a yellow pasty residue.The solid was re-dissolved in toluene (70 mL) at 80° C. and filteredhot. The toluene was evaporated to afford pure(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ (2.35 g, 74%).

Type 1 Polymerization Catalysts Based on(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ (1a) or(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ (1b); Comparative: without catalystmodifier present

Type 1a) To a slurry of dehydrated silica (361.46 g) in toluene (1400mL) was added a 10 wt % MAO solution (1004.41 g of 4.5 wt % Al intoluene) over 35 minutes. The vessel containing the MAO was rinsed withtoluene (2×50 mL) and added to the reaction mixture. The resultantslurry was stirred with an overhead stirrer assembly (200 rpm) for 2hours at ambient temperature. To this slurry was added a toluene (˜100mL) solution of (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ (8.47 g) over10 minutes. This solution may need to be gently heated to 45° C. for abrief period (5 minutes) to fully dissolve the molecule. The vesselcontaining the molecule was rinsed with toluene (2×10 mL) and added tothe reaction mixture. After stirring for 2 hours (200 rpm) at ambienttemperature the slurry was filtered, washed with pentane (2×200 mL) anddried in vacuo to less than 1.5 wt % residual volatiles. The solidcatalyst was isolated and stored under nitrogen until further use. Type1 b) In a glovebox, into a 2 L, three-neck round bottom flask equippedwith an overhead stirrer was added 150 mL toluene. While the solvent wasstirred, 38.894 g of dehydrated silica was added. Next, 107.940 g of aMAO in toluene solution containing 4.5 wt % Al was added into the flaskby cannula over a period of about 15 minutes while stirring wasmaintained. The MAO solution container was rinsed two times, each with25 mL toluene and the rinses were added into the flask. The slurry wasstirred for 1 hour at room temperature. A solution of 0.944 g(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ complex in 10 mL toluene was thenadded into the flask over a period of about 10 minutes. The metalcomplex solution container was rinsed three times, each with about 6 mLtoluene and the rinses were added into the flask. The slurry was stirredfor 2 hours at ambient temperature. The catalyst slurry was poured intoa fritted funnel, which was fitted onto a filter flask, and reducedpressure was then applied to the filter flask to separate the reactionsolvent. Toluene (25 mL) was added to the filter cake and stirred with aspatula to obtain a well dispersed slurry. Reduced pressure was thenapplied to the filter flask to remove the wash solvent. A second toluenewash was done and reduced pressure applied to remove solvent. Pentane(50 mL) was added to the filter cake and stirred with spatula to obtaina well dispersed slurry. Reduced pressure was then applied to the filterflask to remove wash solvent. A second pentane wash was done and reducedpressure applied to remove solvent until the filter cake appears to bedry. The filter cake was then transferred to a 1 L round-bottomed flaskand the catalyst was dried by applying reduced pressure to the flaskuntil a pressure of about 300 mTorr was obtained.

Type 2 Polymerization Catalysts Based on(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)₂ (2a, 2b, 2c, 2d, 2f) or(1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂ (2e); Inventive: with catalystmodifier present

Type 2a) 1.5 wt % Atmer-163. To a pentane (400 mL) slurry of thecatalyst prepared as above (100.17 g of Catalyst Type 1a) was added neatAtmer-163 (1.55 g). The slurry was stirred with an overhead stirrerassembly (200 rpm) for 30 minutes at ambient temperature at which pointvolatiles were removed in vacuo while heating to 30° C. The resultantcatalyst was dried to less than 1.5 wt % residual volatiles, isolatedand stored under nitrogen until further use. Type 2b) 1.5 wt %Armostat-1800. To a slurry of dehydrated silica (58.54 g) in toluene(240 mL) was added a 10 wt % MAO solution (161.89 g of 4.5 wt % Al intoluene) over 35 minutes. The vessel containing the MAO was rinsed withtoluene (2×25 mL) and added to the reaction mixture. The resultantslurry was stirred with an overhead stirrer assembly (200 rpm) for 2hours at ambient temperature. To this slurry was added a toluene (35 mL)solution of (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ (0.91 g) over 10minutes. This solution may need to be gently heated to 45° C. for abrief period (5 minutes) to fully dissolve the molecule. The vesselcontaining the molecule was rinsed with toluene (2×10 mL) and added tothe reaction mixture. After stirring for 2 hours (200 rpm) at ambienttemperature a toluene (20 mL) solution of Armostat-1800 (1.37 g) wasadded to the slurry which was further stirred for 30 minutes. The slurrywas decanted, stirred with pentane (100 mL) for 30 minutes and thendecanted once again. This step was repeated once more before thecatalyst was dried in vacuo to less than 1.5 wt % residual volatiles.The solid catalyst was isolated and stored under nitrogen until furtheruse. Type 2c) 2.5 wt % Armostat-1800. A polymerization catalystcontaining 2.5 wt % of Armostat-1800 was made similarly to Type 2b aboveexcept that the relative amount of Armostat-1800 added was increased togive 2.5 weight percent of catalyst modifier based on the combinedweight of the phosphinimine catalyst, the support and the cocatalyst.Type 2d) 3.5 wt % Armostat-1800. A polymerization catalyst containing3.5 wt % of Armostat-1800 was made similarly to Type 2b above exceptthat the relative amount of Armostat-1800 added was increased to give3.5 weight percent of catalyst modifier based on the combined weight ofthe phosphinimine catalyst, the support and the cocatalyst. Type 2e) 2.5wt % Armostat-1800. In a 3 L, three-neck round bottom flask equippedwith an overhead stirrer was added toluene (320 mL). While the stirrerwas maintained at 200 rpm, dehydrated silica (79.702 g) was added. A 10wt % MAO in toluene solution (174.607 g) was added into the flask bycannula over a period of about 15 minutes while stirring was maintained.The MAO solution container was rinsed with toluene (2×25 mL), and therinses were added into the flask. The slurry was stirred for 2 hours atroom temperature. The complex, (1-C₆F₅CH₂—Indenyl)((t-Bu)₃P═N)TiCl₂,(1.996 g) was then added into the flask in solid form over a period ofabout 5 minutes. The slurry was stirred for 2 hours at ambienttemperature. A 15 wt % Armostat-1800 in toluene solution (16.762 g) wasadded into the flask over a period of 3 minutes. The container wasrinsed with toluene (2×5 mL), and the rinses were added in the flask.The slurry was further stirred at ambient temperature for 30 minutes.The catalyst slurry was poured into a fritted funnel, which was fittedonto a filter flask, and reduced pressure applied to the filter flask toseparate the reaction solvent. Toluene (150 mL) was added to the filtercake and stirred with a spatula to obtain a well dispersed slurry.Reduced pressure was then applied to the filter flask to remove the washsolvent. A second toluene wash was done and reduced pressure applied toremove solvent. Pentane (150 mL) was added to the filter cake andstirred with spatula to obtain a well-dispersed slurry. Reduced pressurewas then applied to the filter flask to remove wash solvent. A secondpentane wash was done and reduced pressure applied to remove solventuntil the filter cake appears to be dry. The filter cake was thentransferred to a 2 L round-bottomed flask and the catalyst was dried byapplying reduced pressure to the flask until 315 mTorr was obtained.Type 2f) A polymerization catalyst containing 2.7 wt % of Armostat-1800was made similarly to Type 2b above except that the relative amount ofArmostat-1800 added was increased to give 2.7 weight percent of catalystmodifier based on the combined weight of the phosphinimine catalyst, thesupport and the cocatalyst.

General Polymerization Conditions

Continuous ethylene/1-hexene gas phase copolymerization experiments wereconducted in a 56.4 liter technical scale reactor (TSR) in continuousgas phase operation (for an example of a TSR reactor set up see EuropeanPatent Application No. 659,773A1). Ethylene polymerizations were run at80° C. with a total operating pressure of 300 pounds per square inchgauge (psig). Gas phase compositions for ethylene, 1-hexene and hydrogenwere controlled via closed-loop process control to values of 35 to 51,0.5 to 1.7 and 0.018 to 0.042 mole percent, respectively. Nitrogenconstituted the remainder of the gas phase mixture (approximately 49mole %). Typical production rate for these conditions was 2.0 to 3.0 kgof polyethylene per hour. Triethylaluminum (TEAL) was fed to the reactorcontinuously, as a 0.25 wt % solution in hexane (solution fed at about10 mL/hr) in order to scavenge impurities. The residence time in thereactor is held at 1.5 to 3.0 hr, with a production rate range from 1.5to 2.7 kg/hr.

The catalyst metering device used for administering catalyst to thereactor is equipped with a static probe that measures electrostaticcharge carried by the solid material passing through a monitored tubeleading catalyst to the reactor.

Polymer Analysis

Melt index, I₂, in g/10 min was determined on a Tinius Olsen Plastomer(Model MP993) in accordance with ASTM D1238 condition F at 190° C. witha 2.16 kilogram weight. Melt index, I₁₀, was determined in accordancewith ASTM D1238 condition F at 190° C. with a 10 kilogram weight. Highload melt index, I₂₁, in g/10 min was determined in accordance with ASTMD1238 condition E at 190° C. with a 21.6 kilogram weight.

Polymer density was determined in grams per cubic centimeter (g/cc)according to ASTM D792.

Molecular weight information (M_(w), M_(n) and M_(z) in g/mol) andmolecular weight distribution (M_(w)/M_(n)), and z-average molecularweight distribution (M_(Z)/M_(W)) were analyzed by gel permeationchromatography (GPC), using an instrument sold under the trade name“Waters 150c”, with 1,2,4-trichlorobenzene as the mobile phase at 140°C. The samples were prepared by dissolving the polymer in this solventand were run without filtration. Molecular weights are expressed aspolyethylene equivalents with a relative standard deviation of 2.9% forthe number average molecular weight (“Mn”) and 5.0% for the weightaverage molecular weight (“Mw”). Polymer sample solutions (1 to 2 mg/mL)were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) androtating on a wheel for 4 hours at 150° C. in an oven. The antioxidant2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in orderto stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Sample solutions were chromatographed at 140°C. on a PL 220 high-temperature chromatography unit equipped with fourShodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobilephase with a flow rate of 1.0 mL/minute, with a differential refractiveindex (DRI) as the concentration detector. BHT was added to the mobilephase at a concentration of 250 ppm to protect the columns fromoxidative degradation. The sample injection volume was 200 mL. The rawdata were processed with Cirrus GPC software. The columns werecalibrated with narrow distribution polystyrene standards. Thepolystyrene molecular weights were converted to polyethylene molecularweights using the Mark-Houwink equation, as described in the ASTMstandard test method D6474.

The peak melting point (T_(m)) and percent of crystallinity of thepolymers were determined by using a TA Instrument DSC Q1000 ThermalAnalyzer at 10° C./min. In a DSC measurement, a heating-cooling-heatingcycle from room temperature to 200° C. or vice versa was applied to thepolymers to minimize the thermo-mechanical history associated with them.The melting point and percent of crystallinity were determined by theprimary peak temperature and the total area under the DSC curverespectively from the second heating data. The peak melting temperatureT_(m) is the higher temperature peak, when two peaks are presented in abimodal DSC profile (typically also having the greatest peak height).

A compression molded film of 0.0035 inches was extracted at 50° C. inhexane for 2 hours. The sample was re-weighed and the extractablecontent was determined from the relative change in sample weightaccording to ASTM D5227.

The branch frequency of copolymer samples (i.e., the short chainbranching, SCB per 1000 carbons) and the C₆ comonomer content (in wt %)was determined by Fourier Transform Infrared Spectroscopy (FTIR) as perthe ASTM D6645-01 method. A Thermo-Nicolet 750 Magna-IRSpectrophotometer equipped with OMNIC version 7.2a software was used forthe measurements.

The determination of branch frequency as a function of molecular weight(and hence the comonomer distribution profile) was carried out usinghigh temperature Gel Permeation Chromatography (GPC) and FT-IR of theeluent. Polyethylene standards with a known branch content, polystyreneand hydrocarbons with a known molecular weight were used forcalibration.

To determine CDBI, a solubility distribution curve is first generatedfor the copolymer. This is accomplished using data acquired from theTREF technique. This solubility distribution curve is a plot of theweight fraction of the copolymer that is solubilized as a function oftemperature. This is converted to a cumulative distribution curve ofweight fraction versus comonomer content, from which the CDBI isdetermined by establishing the weight percentage of a copolymer samplethat has a comonomer content within 50% of the median comonomer contenton each side of the median. The weight percentage of a higher densityfraction, (i.e. the wt % eluting from 90-105° C.), is determined bycalculating the area under the TREF curve at an elution temperature offrom 90 to 105° C. The weight percent of copolymer eluting below 40° C.can be similarly determined. For the purpose of simplifying thecorrelation of composition with elution temperature, all fractions areassumed to have a Mn-15,000, where Mn is the number average molecularweight of the fraction. Any low molecular weight fractions presentgenerally represent a trivial portion of the polymer. The remainder ofthis description maintains this convention of assuming all fractionshave Mn-15,000 in the CDBI measurement.

Temperature rising elution fractionation (TREF) method. Polymer samples(50 to 150 mg) were introduced into the reactor vessel of acrystallization-TREF unit (Polymer ChAR™). The reactor vessel was filledwith 20 to 40 ml 1,2,4-trichlorobenzene (TCB), and heated to the desireddissolution temperature (e.g., 150° C.) for 1 to 3 hours. The solution(0.5 to 1.5 ml) was then loaded into the TREF column filled withstainless steel beads. After equilibration at a given stabilizationtemperature (e.g. 110° C.) for 30 to 45 minutes, the polymer solutionwas allowed to crystallize with a temperature drop from thestabilization temperature to 30° C. (0.1 or 0.2° C./minute). Afterequilibrating at 30° C. for 30 minutes, the crystallized sample waseluted with TCB (0.5 or 0.75 mL/minute) with a temperature ramp from 30°C. to the stabilization temperature (0.25 or 1.0° C./minute). The TREFcolumn was cleaned at the end of the run for 30 minutes at thedissolution temperature. The data were processed using Polymer ChARsoftware, Excel spreadsheet and TREF software developed in-house.

The TREF procedure described above is well known to persons skilled inthe art and can be used to determine: the overall TREF profile, CDBI,copolymer wt % below 40° C., and copolymer wt % from 90° C. to 105° C.

Gel Count Procedure

An in-lab OCS gel measurement system, which consists of an OCS gelcamera, FSA 100 film scanning unit, image analysis software, cast lineextruder and chill roll windup setup, is used to determine the amount ofgels in a 1.0 to 2.0 mil cast film. For a gel count measurement, apolymer sample is added into a 20 mm extruder with a mixing screw of 3:1or 4:1 compression ratio and run at 60 rpm. The haul-off speed and chillroll temperature of the cast film line are set at 8.0 m/min and 23 to30° C. respectively. The pictures of cast film are taken by an OCScamera continuously and the film scanning unit with image analysissoftware is used to monitor the gel data in the pictures. The gel countsin a cast film are defined as the total area of defects per total areameasured and reported as a total ppm value.

Polymerization Results

Examples 1, 3, 5, 6, 13 and 16 Comparative Baseline Runs

The Type 1 Catalysts (each of the Type 1 Catalysts 1a and 1 b, areprepared as described above) were placed under a N2 blanket and using adry catalyst feeder, a small shot of supported catalyst was continuouslyadded to a technical scale reactor via a feeding tube. Equilibriumpolymerization conditions were established after a period of 4 residencetimes. Once equilibrium conditions were established, the static level inthe reactor was measured over 6 hours using a static probe (CorreflowElectrostatic Monitor 3410™ available from Progression). The staticprobe was located within the polymerization reactor. The reactortemperature was also measured. Several similar runs were carried out atdifferent times to establish baseline run conditions prior to running aninventive example (see “baseline” Run Nos. 1, 3, 5, 6, 13 and 16 ofTable 1). Static of the solid catalyst entering the reactor was alsomeasured within the catalyst metering area over the 6 hour period.Relevant data for these examples are provided in Table 1.

Examples 2, 4, 7-12, and 17 Inventive Runs

In each polymerization run, a Type 2 polymerization catalyst (each ofthe Type 2 Catalysts 2a-2e, are prepared as described above usingvarious amounts of a catalyst modifier) was placed under a N2 blanketand using a dry catalyst feeder, a small shot of supported catalyst wascontinuously added to a technical scale reactor via a feeding tube.Equilibrium polymerization conditions were established after a period of4 residence times. Once equilibrium conditions were established, thestatic level in the reactor was measured over 6 hours using a staticprobe (Correflow Electrostatic Monitor 3410 available from Progression).The static probe was located within the polymerization reactor. Duringthis time reactor temperature was also measured. Polymerization runsusing Type 2 catalysts are inventive runs (see “inventive”polymerization Run Nos. 2, 4, 7-12 and 17 in Table 1) and were carriedout soon after establishing appropriate baseline conditions. Static ofthe solid catalyst entering the reactor was also measured within thecatalyst metering area over the 6 hour period. An examination of thepolymer product obtained during each of these runs revealed a freeflowing powder without significant chunks or strings. Relevant data forthese examples are provided in Table 1.

Examples 14 and 15 Comparative Runs

To provide a comparison between adding catalyst modifier directly to thereactor and including a catalyst modifier in the catalyst formulation,polymerization runs were conducted in which the catalyst modifier wasadded to the reactor directly, instead of including the catalystmodifier in the polymerization catalyst (see “comparative” Run Nos. 14and 15). These examples were conducted in a manner analogous to Example1, except that once equilibrium polymerization conditions wereestablished, a catalyst modifier was fed to the reactor. The catalystmodifier was Atmer-163 which was diluted in hexanes to give a 1% byweight mixture and added via a manifold, into the reactor. In Example14, 25 ppm of Atmer-163 (per mass of polymer produced) was fed to thereactor. Once steady state was achieved, the reaction was held constantfor another 3-4 residence times, and then the static level in thereactor was measured over 6 hours. Reactor temperature was measured andthe static of the catalyst entering the reactor was measured within thecatalyst metering area over the 6 hour period. In Example 15, the levelof Atmer-163 fed to the reactor was increased from 25 ppm to 100 ppm(based on the weight of the polymer produced) and then the static levelwas measured over 6 hours. Reactor temperature and the static of thecatalyst entering the reactor were measured within the catalyst meteringarea over the 6 hour period. An examination of the polymer productobtained during Atmer-163 addition revealed a free flowing powderwithout significant chunks or strings. Relevant data for these examplesare provided in Table 1.

Examples 18-21

To provide a comparison between having a catalyst modifier only presentin the polymerization catalyst with having the catalyst modifier presentin both the polymerization catalyst as well as being fed directly to thereactor, polymerization runs were conducted in which the catalystmodifier was added to the reactor directly, in addition to including thecatalyst modifier in the polymerization catalyst: compare polymerizationRun No. 18 with polymerization Run No. 19 in Table 1. To examine whetherchanging the nature of the catalyst modifier which is fed directly tothe reactor, would impact polymerization performance, polymerizationruns were also performed using the known antistatic compoundSTATSAFE-6633™ in place of Atmer-163: compare polymerization Run No 20with polymerization Run No. 21 in Table 1.

TABLE 1 Static Level, Catalyst Productivity and Reactor TemperatureRange Examples Catalyst Catalyst Productivity Catalyst Reactor Temp.(Poly. Run Catalyst Modifier in Modifier fed (g poly/g Static StaticStandard No.)¹ Type Catalyst to Reactor cat) Level² Level³ Deviation⁴  1(baseline) Type 1a none none 3209 0.045 0.71 1.2  2 (inventive) Type 2a1.5 wt % none 4423 0.020 0.39 0.4 Atmer-163  3 (baseline) Type 1a nonenone 4900 0.031 0.63 0.7  4 (inventive) Type 2b 1.5 wt % none 5346 0.0160.86⁵ 0.5 Armostat- 1800  5 (baseline) Type 1a none none 3909 0.041 0.430.8  6 (baseline) Type 1a none none 4043 0.029 0.42 0.7  7 (inventive)Type 2b 1.5 wt % none 4238 0.022 0.26 0.4 Armostat- 1800  8 (inventive)Type 2c 2.5 wt % none 6842 0.023 0.87⁶ 0.3 Armostat- 1800  9 (inventive)Type 2c 2.5 wt % none 5418 0.023 0.32 0.3 Armostat- 1800 10 (inventive)Type 2b 1.5 wt % none 5328 0.013 0.26 0.5 Armostat- 1800 11 (inventive)Type 2d 3.5 wt % none 4751 0.019 0.34 0.3 Armostat- 1800 12 (inventive)Type 2d 3.5 wt % none 5000 0.016 0.58⁷ 0.6 Armostat- 1800 13 (baseline)Type 1a none none 3955 0.019 0.47 — 14 (comparative) Type 1a none 25 ppm3653 0.026 0.31 — Atmer-163 15 (comparative) Type 1a none 100 ppm 2760.027 0.29 — Atmer-163 16 (baseline) Type 1b none none 2300 0.023 0.230.41 17 (inventive) Type 2e 2.5 wt % none 3000 0.046 0.14 0.22 Armostat-1800 18 (baseline) 2f 2.7 wt % none 3704 — 0.39 0.4 Armostat- 1800 19(inventive) 2f 2.7 wt % 37 ppm 2268 — 0.16 0.3 Armostat- Atmer-163 180020 (baseline) 2f 2.7 wt % none 2330 — 0.493 1.2 Armostat- 1800 21(comparative) 2f 2.7 wt % 93 ppm 3766 — 0.506 0.6 Armostat- Statsafe1800 6633 Note ¹Pol. Run Nos 1-15, and 18-21 use a polymerizationcatalyst based on the phosphinimine complex(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂; Pol. Run Nos 16 and 17 use apolymerization catalyst based on the phosphinimine complex(1-C₆F₅CH₂-Indenyl)((t-Bu)₃P═N)TiCl₂. Note ²The static level of thecatalyst entering the reactor was measured by using a Correstat 3410static probe over a 6 hour period (or a 12 hour period for Pol Run Nos16 and 17). To obtain this value, a static signal, in nanoamps, isrecorded each second in the catalyst metering tube. These signals aretransformed into positive values by taking the absolute value of eachnumber. The sum of the absolute values is divided by the number ofseconds used to calculate the sum; this number is reported in Table 1.Note ³The static level of solids in the reactor was measured with aCorrestat 3410 static probe over a 6 hour period (or a 12 hour periodfor Pol Run Nos 16 and 17). To obtain this value, a static signal, innanoamps, is recorded each second at the reactor wall. These signals aretransformed into positive values by taking the absolute value of eachnumber. The sum of the absolute values is divided by the number ofseconds used to calculate the sum; this number is reported in Table 1.Note ⁴The standard deviation in temperature. Standard deviation of thereactor temperature is a way to quantify how much the reactortemperature fluctuates from the mean temperature or control temperature.A smaller standard deviation means smaller temperature fluctuationsaround the control temperature. A larger standard deviation means largertemperature fluctuations around the control temperature. In the data setgenerated for the patent, the standard deviation was calculated over 10hours of steady state operation (or a 12 hour period from Pol. Run Nos16 and 17). Note ⁵This run had a higher than expected reactor staticreading for unknown reasons. We note however, that the catalyst staticlevel and the size of the temperature excursion are both low relative tothe baseline case (Run. No. 3). Note ⁶An unexpected increase in staticsuddenly occurred during this run. Examination of the polymer showed asmall amount of roped material which may have artificially increased theoverall static measurement within the last 6 hours of this run. Anexamination of the static levels prior to the static spike wasconsistent with an overall static measurement of 0.49 (i.e. over theprevious 6 hours). Note ⁷An ethylene pressure supply problem createdpressure swings in the reactor which may have impacted the reactorstatic measurement.

The data in Table 1 shows that the inclusion of a catalyst modifier inthe phosphinimine based polymerization catalyst can improve catalystproductivity, and that to improve productivity, the preferred amounts ofcatalyst modifier added are somewhere from about 0.5 wt % to about 4.0wt % based on the weight of the polymerization catalyst. FIG. 1 alsoshows how optimizing the amount of catalyst modifier can increase thecatalyst productivity. The improvement in catalyst productivity wasobserved regardless of whether the phosphinimine catalyst used to makethe polymerization catalyst included a substituted cyclopentadienylligand (e.g., (1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂) or asubstituted indenyl ligand (e.g., (1-C₆F₅CH₂-Indenyl)((t-Bu)₃P═N)TiCl₂).

The data provided in Table 1 shows that inclusion of a catalyst modifierwithin the polymerization catalyst reduced at least one of: reactorstatic level, catalyst static level, and reactor temperature excursionsrelative to the polymerization catalyst not treated with a catalystmodifier. With the exception of Run No. 8 (in which a small amount ofpolymer rope was formed; see Note 6) visual examination of all polymerproducts obtained using a Type 2 catalyst revealed products which werefree flowing powders without significant chunks or strings. Hence, thedata show that reactor continuity and operability improve when acatalyst modifier is included in the polymerization catalystformulation.

Inclusion of the catalyst modifier in the polymerization catalystgenerally decreases the level of static measured in the reactor.Although there were a few exceptions to this trend (see polymerizationRun Nos. 4, 8, 12 and corresponding Notes 5, 6 and 7 respectively), wenote that in virtually all cases the catalyst static measured decreasedwhen a Type 2 catalyst was used relative to a Type 1 catalyst (theexception was polymerization Run No. 17). In all inventive Examplesusing a Type 2 catalyst (treated with a catalyst modifier), the reactortemperature excursions were smaller than when a Type 1 catalyst (nottreated with a catalyst modifier) was used.

For plots of reactor static observed over time for polymerization runsusing catalysts with and without catalyst modifier treatment see FIGS.2, 3, 4, 5, 6, 7, 10 and 11 which correspond to Polymerization Run Nos.1, 2, 6, 7, 9, 11, 16 and 17 respectively. For plots of reactor staticobserved over time for polymerization runs using the Type 1a catalyst(without catalyst modifier treatment), but where the catalyst modifierwas not added or added directly to the reactor see FIGS. 8 and 9 whichcorrespond to Polymerization Run Nos. 13 and 14 respectively.

The data in Table 1 also includes a comparison between adding thecatalyst modifier to the catalyst and adding the catalyst modifierdirectly to the reactor. It is clear that although addition of thecatalyst modifier directly to the reactor improves static levels andreactor operability relative to baseline conditions, it also negativelyimpacts the catalyst productivity to some degree, especially at higherloadings. Hence, the data in Table 1 indicate that only inclusion of thecatalyst modifier within the polymerization catalyst formulationprovides the dual improvement: higher catalyst productivity and betterreactor operability.

In addition to improvements in reactor operability, we have found thatinclusion of a catalyst modifier in the polymerization catalyst (oraddition of catalyst modifier directly to the reactor) may dramaticallyaffect copolymer product architecture while not significantly changingthe polymer density or melt index. The polymer properties of copolymersisolated from polymerization Run Nos. 2, 4, 6, 9, 11, 14, 16 and 17, areprovided below in Table 2.

Finally, the data in Table 1 also includes a comparison between addingthe catalyst modifier to the polymerization catalyst and adding thecatalyst modifier both to the polymerization catalyst and directly tothe reactor. It is clear that addition of the catalyst modifier directlyto the reactor in addition to having the catalyst modifier present inthe polymerization catalyst further improves static levels and reactoroperability, relative to just having the catalyst modifier in thepolymerization catalyst, but this comes at the expense of lost catalystproductivity to some degree, especially at higher catalyst modifierloadings to the reactor. Compare Poly. Run No. 18 with Poly. Run No. 19in Table 1. As a result, when adding the catalyst modifier directly tothe reactor, it may be preferable to feed it in an amount of about 50ppm or less.

In contrast to the results observed with Atmer-163, when feedingSTATSAFE-6633™ directly to the reactor, there is no significant furtherdecrease in the static levels in the reactor. Instead, there is anappreciable rise in catalyst productivity. Compare Poly. Run No. 20 withPoly. Run No. 21 in Table 1.

TABLE 2 Polymer Properties Poly. Run No. 6 14 2 4 9 11 16 17 CatalystType 1a Type 1a Type 2a Type 2b Type 2c Type 2d Type 1b Type 2e CatalystNone none 1.5 wt % 1.5 wt % 2.5 wt % 3.5 wt % none 2.5 wt % Modifier inAtmer- Armostat- Armostat- Armostat- Armostat- Catalyst 163 1800 18001800 1800 Catalyst None 25 ppm None none none none none none Modifierfed Atmer- to Reactor 163 Density 0.9182 0.9174 0.9189 0.9180 0.91860.9185 0.923 0.92 (g/cc) I₂ (g/10 min) 1.01 1.03 0.89 1.03 0.90 0.93 0.60.54 I₁₀/I₂ 5.78 5.63 5.76 5.64 5.64 5.66 9.55 10.6 I₂₁/I₂ 16.3 15.916.7 15.8 14.1 16.1 34.1 43.5 CDBI (wt %) 50.2 58.2 55.2 57.9 61.4 58.146 47.2 TREF (90- 20.4 15.3 20.9 16.7 15.4 17.0 25 20 105° C., wt %) Mn52879 55077 50825 47455 53940 57167 23637 25053 Mw 103750 104231 109275100157 106495 106771 114502 120821 Mz 177076 179401 205446 164387 177080174086 330614 372081 Mw/Mn 1.96 1.89 2.15 2.11 1.97 1.87 4.84 4.82SCB/1000 C's 10.4 10.9 9.6 10.1 10.0 10.3 10.9 13.3 mole % of C6 2.1 2.21.9 2.0 2.0 2.1 2.2 2.7 wt % of C6 6.00 6.20 5.5 5.80 5.70 5.90 6.3 7.6Comonomer 1-hexene 1-hexene 1-hexene 1-hexene 1-hexene 1-hexene 1-hexene1-hexene Comonomer Normal flat reversed reversed reversed partiallyslightly highly Profile reversed reversed reversed (GPC-FTIR) Peak 118.5117.0 119.0 117.6 117.3 117.3 107.5/121.4 121.1 Melting Temperature (°C.) % 44.2 44.5 45.3 47.4 44.5 44.6 47.4 44.4 Crystallinity Hexane 0.210.19 0.22 0.22 0.27 0.26 0.52 0.72 Extractables (%) Poly. Run No. 18 1920 21 Catalyst Type 2f Type 2f Type 2f Type 2f Catalyst 2.7 wt % 2.7 wt% 2.7 wt % 2.7 wt % Modifier in Armostat- Armostat- Armostat- Armostat-Catalyst 1800 1800 1800 1800 Catalyst None 37 ppm None 93 ppm Modifierfed Atmer- Statsafe- to Reactor 163 6633 Density 0.918 0.918 0.91720.918 (g/cc) I₂ (g/10 min) 1.23 1.21 0.9 0.92 I₁₀/I₂ 5.63 5.63 5.64 5.64I₂₁/I₂ 15.5 15.5 15.6 14.9 CDBI (wt %) 72.5 72.5 68.5 70.2 TREF (90- 9.19.6 12.8 12.1 105° C., wt %) Mn 54121 54917 63516 58751 Mw 99993 102318119688 118187 Mz 162970 164347 201648 224608 Mw/Mn 1.85 1.86 1.88 2.01SCB/1000 C's 10.9 10.6 10.4 10.2 mole % of C6 2.2 2.1 2.1 2 wt % of C66.3 6.1 6 5.9 Comonomer 1-hexene 1-hexene 1-hexene 1-hexene ComonomerSlightly Reverse Reverse reverse Profile reverse (GPC-FTIR) Peak 108.7/108.7/ 107.9/ 108.0/ Melting 115.6 115.9 117.8 117.3 Temperature (° C.)% 44.3 44.9 44.4 45.8 Crystallinity Hexane 0.11 0.16 0.21 0.15Extractables (%)

The data in Table 2 shows that the “composition distribution” may bedifferent for copolymers made with a Type 2 catalyst relative tocopolymers made with a Type 1 catalyst. Indices which characterizechanges in “composition distribution” of the ethylene copolymer includechanges to one or more of the following: A) the composition distributionbreadth index (CDBI) of the ethylene copolymer as measured usingtemperature rising elution fractionation (TREF) methods; B) the weightpercent of a higher temperature eluting material (i.e., from 90° C. to105° C.) observed in TREF profile obtained for the ethylene copolymer;and C) the comonomer distribution profile (i.e. the comonomerincorporation vs. molecular weight) of the ethylene copolymer asmeasured by gel permeation chromatography with Fourier transformdetection (GPC-FTIR).

Examination of the data in Table 2 (compare for example Run No. 6 withRun Nos. 4, 9 and 11) shows that the amount of copolymer (in weightpercent) which elutes at 90-105° C. in a TREF analysis is lower when aType 2 catalyst (treated with Armostat-1800) is used than when a Type 1catalyst (no catalyst modifier) is used to copolymerize ethylene with1-hexene (an exception occurred during Run No. 2 using a Type 2 catalysttreated with Atmer-163 where the amount of copolymer (in weight percent)which eluted at 90-105° C. in a TREF analysis remained largelyunchanged). These results indicate that inclusion of the catalystmodifier in the polymerization catalyst improves short chain branching(i.e., comonomer) homogeneity. This fact is further evidenced by theincrease in CDBI observed with all the Type 2 catalysts tested.Comparison of Run No. 6 with Run Nos. 2, 4, 9 and 11 in Table 2 showsthat, for every case, the CDBI is higher when a Type 2 catalyst is usedrelative to a Type 1 catalyst. In fact, the CDBI is increased by atleast 5% in each case and more than 10% for the copolymer obtained inRun No. 9. The comonomer distribution profile is also changed when acatalyst modifier is present in the polymerization catalyst. When a Type2 catalyst is employed, the amount of comonomer incorporation at highermolecular weights relative to lower molecular weights (as measured byGPC-FTIR) is higher than the amount of comonomer incorporation at highermolecular weights relative to lower molecular weights when a Type 1catalyst is used (Table 2 shows that the comonomer distribution changesfrom a normal profile to a flat, reversed or partially reversed profile,or from a slightly reversed profile to a highly reversed profile, when acatalyst modifier is present in the polymerization catalyst). Increasingthe amount of comonomer incorporation at higher molecular weights mayimprove polymer end use properties such as dart impact, punctureresistance, optical properties, and hot tack or seal performance.

The data provided in Table 2 also shows that the ethylene copolymer madewhen a catalyst modifier is both fed to a reactor and present in thepolymerization catalyst is similar to the ethylene copolymer made when acatalyst modifier is only present in the polymerization catalyst:compare the copolymer made in Poly. Run No 18 (baseline) with copolymermade in Pol Run No. 19, in Table 2.

Finally we note that inclusion of a catalyst modifier in thepolymerization catalyst improved the gel properties of cast film madefrom ethylene copolymers obtained with such catalysts (i.e. Type 2Catalysts). The gel properties of copolymers isolated from selectedpolymerization runs are provided below in Table 3.

TABLE 3 Gels in Cast Film OCS Gel Catalyst Modifier Catalyst ModifierCount Poly. Run No. in Catalyst fed to Reactor (ppm) 5 none None 83 6none None 141 7 1.5 wt % None 9 Armostat-1800 9 2.5 wt % None 6Armostat-1800 11 3.5 wt % None 7 Armostat-1800 14 none 25 ppm 13Atmer-163

Table 3 shows that use of a Type 1 Catalyst (no catalyst modifier) givescopolymer product which when cast into film has high gels counts (83 and141 for baseline runs 5 and 6) while use of a Type 2 Catalyst (includesa catalyst modifier) gives copolymer product which has a gel count ofbelow 10 when cast into film.

What is claimed is:
 1. A polymerization process to make an ethylenecopolymer, the process comprising contacting ethylene and at least onealpha olefin with a polymerization catalyst in a gas phase reactor, thepolymerization catalyst comprising: i) a phosphinimine catalyst, ii) aninert support, iii) a cocatalyst, and iv) a catalyst modifier; whereinthe catalyst modifier is present in from 0.25 to 6.0 weight percentbased on the weight of i), ii) and iii) of the polymerization catalystand comprises a compound having the formula: R¹R² _(x)N((CH₂)_(n)OH)_(y)where R¹ is a hydrocarbyl group having from 5 to 30 carbon atoms, R² ishydrogen or a hydrocarbyl group having from 1 to 30 carbon atoms, x is 1or 0; when x is 1, y is 1 and n is an integer from 1 to 30; when x is 0,y is 2 and each n is independently an integer from 1 to 30; wherein thephosphinimine catalyst has the formula: (L)((t-Bu)₃P═N)TiX₂, where L isa cyclopentadienyl ligand, a substituted cyclopentadienyl ligand, anindenyl ligand, or a substituted indenyl ligand; and X is an activatableligand; and wherein the process further comprises feeding the catalystmodifier to the gas phase reactor in an amount of 50 ppm or less basedon the weight of the ethylene copolymer produced.
 2. The process ofclaim 1 wherein the catalyst modifier present in the polymerizationcatalyst and fed to the gas phase reactor comprises at least onecompound represented by the formula: R¹N((CH₂)_(n)OH)((CH₂)_(m)OH) whereR¹ is a hydrocarbyl group having from 5 to 30 carbon atoms, and n and mare integers from 1 to
 20. 3. The process of claim 1 wherein thecatalyst modifier present in the polymerization catalyst and fed to thegas phase reactor comprises at least one compound represented by theformula: R¹N((CH₂)_(n)OH)₂ where R¹ is a hydrocarbyl group having from 6to 30 carbon atoms, and each n is independently an integer from 1-20. 4.The process of claim 1 wherein the catalyst modifier present in thepolymerization catalyst and fed to the gas phase reactor comprises atleast one compound represented by the formula: R¹N((CH₂)_(n)OH)₂ whereR¹ is a hydrocarbyl group having from 6 to 30 carbon atoms, and each nis 2 or
 3. 5. The process of claim 1 wherein the catalyst modifierpresent in the polymerization catalyst and fed to the gas phase reactorcomprises at least one compound represented by the formula:R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having from 8 to 22carbon atoms.
 6. The process of claim 1 wherein the catalyst modifierpresent in the polymerization catalyst and fed to the gas phase reactorcomprises a compound represented by the formula: C₁₈H₃₇N(CH₂CH₂OH)₂. 7.The process of claim 1 wherein the catalyst modifier present in thepolymerization catalyst and fed to the gas phase reactor comprisescompounds represented by the formulas: C₁₃H₂₇N(CH₂CH₂OH)₂ andC₁₅H₃₁N(CH₂CH₂OH)₂.
 8. The process of claim 1 wherein the catalystmodifier present in the polymerization catalyst and fed to the gas phasereactor is a mixture of compounds represented by the formula:R¹N(CH₂CH₂OH)₂ where R¹ is a hydrocarbyl group having from 8 to 18carbon atoms.
 9. The process of claim 1 wherein the phosphiniminecatalyst has the formula: (L)((t-Bu)₃P═N)TiX₂, where L is a substitutedcyclopentadienyl ligand or a substituted indenyl ligand; and X is anactivatable ligand.
 10. The process of claim 1 wherein the cocatalyst isselected from ionic activators, alkylaluminoxanes and mixtures thereof.11. The process of claim 1 wherein the inert support is silica.
 12. Theprocess of claim 1 wherein the catalyst modifier is present in thepolymerization catalyst in from about 0.5 to about 4.5 weight percentbased on the weight of i), ii) and iii) of the polymerization catalyst.13. The process of claim 1 wherein the catalyst modifier is present inthe polymerization catalyst in from about 1.0 to about 4.0 weightpercent based on the weight of i), ii) and iii) of the polymerizationcatalyst.
 14. The process of claim 1 wherein the amount of catalystmodifier fed to the gas phase reactor is 25 ppm or less based on theweight of the ethylene copolymer produced.